Removal of materials from water

ABSTRACT

Various embodiments relate to methods and systems for removing phosphorus and/or nitrogen from water. A method of removing phosphorus and nitrogen from water includes passing starting material water including nitrogen and phosphorus through an elevated pH phosphorus removal stage. The method includes passing the water through an electrolytic nitrogen removal stage. The method includes passing the water through a galvanic phosphorus removal stage. The water produced by the method has a lower phosphorus concentration and a lower nitrogen concentration than the starting material water.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of International Application No.PCT/US2020/037407, filed Jun. 12, 2020, which claims the benefit ofpriority to U.S. Provisional Patent Application Ser. No. 62/860,433filed Jun. 12, 2019, the disclosure of each of which is incorporatedherein in their entireties by reference.

BACKGROUND

Phosphorus is a common constituent of agricultural fertilizers, manure,and organic wastes in sewage and industrial effluent. It is an essentialelement for plant life, but when there is too much of it in water, itcan cause growth of plants and algae and deplete oxygen from the waterat a rate that is greater than ecosystems can handle and can have severeecological effects including toxic algae blooms, death of native aquaticspecies, and loss of biodiversity (eutrophication). Although variousmethods for removal of phosphorus from water are available, existingmethods can be expensive, inconvenient, inefficient, lack scalability,or can be environmentally unfriendly.

Nitrogen is a common constituent of agricultural fertilizers, manure,and organic wastes in sewage and industrial effluent. It is an essentialelement for plant life. However, when there is too much nitrogen inwater, it can cause growth of plants and algae and can deplete oxygenfrom the water at a rate that is greater than ecosystems can handle,causing severe ecological effects including toxic algae blooms, death ofnative aquatic species, and loss of biodiversity (eutrophication).Simple particulate removal processes such as filtration will removeparticulates and lower the total nitrogen concentration; however, theseprocesses will not lower the concentration of water-soluble forms ofnitrogen. Although various methods for removal of soluble nitrogen fromwater are available, these methods are expensive, complex, and difficultto control.

SUMMARY OF THE INVENTION

In various embodiments, the present invention provides a method ofremoving phosphorus and nitrogen from water. The method includes passingstarting material water including nitrogen and phosphorus through anelevated pH phosphorus removal stage. The elevated pH phosphorus removalstage includes raising pH of the water to greater than or equal to 7.5to precipitate a phosphorus salt from the water. The elevated pHphosphorus removal stage also includes removing the precipitatedphosphorus salt from the water. The method include passing the waterthrough an electrolytic nitrogen removal stage including passing thewater through an electrolytic cell to remove nitrogen from the water asnitrogen gas. The method also includes passing the water through agalvanic phosphorus removal stage including immersing a galvanic cell inthe water to form treated water including a salt that includesphosphorus from the water. The galvanic cell includes an anode includingMg, Al, Fe, Zn, or a combination thereof, and a cathode having adifferent composition than the anode, the cathode including Cu, Ni, Fe,or a combination thereof. The galvanic phosphorus removal stage alsoincludes separating the salt including the phosphorus from the treatedwater. The water produced by the method has a lower phosphorusconcentration and a lower nitrogen concentration than the startingmaterial water.

In various embodiments, the present invention provides a method ofremoving phosphorus and nitrogen from water. The method includes passingstarting material water including nitrogen and phosphorus through anelevated pH phosphorus removal stage. The elevated pH phosphorus removalstage includes raising pH of the water using one or more bases to 8.5 to9.5 to precipitate a phosphorus salt from the water including struvite,calcium phosphate, or a combination thereof. The elevated pH phosphorusremoval stage also includes removing the precipitated phosphorus saltfrom the water. The elevated pH phosphorus removal stage removes 90-98%of reactive phosphorus in the water. The method includes passing thewater through an electrolytic nitrogen removal stage including passingthe water through an electrolytic cell to remove nitrogen from the wateras nitrogen gas. The electrolytic cell includes a cathode includingstainless steel and an anode that includes titanium oxide, rutheniumoxide, and iridium oxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti).Passing the water through the electrolytic nitrogen removal stageremoves 80-100% of ammonia from the water. The method also includespassing the water through a galvanic phosphorus removal stage includingimmersing a galvanic cell in the water to form treated water including asalt that includes phosphorus from the water. The salt includes AlPO₄ ora hydrate thereof, the AlPO₄ including the phosphorus and Al from theanode; aluminum hydroxide or a hydrate thereof, the aluminum hydroxideincluding Al from the anode; or a combination thereof. The galvanic cellincludes an anode including Al, wherein the anode is about 90 wt % toabout 100 wt % Al. The galvanic cell includes a cathode including Cu,wherein the cathode is about 90 wt % to about 100 wt % Cu. The galvaniccell also includes a conductive connector that electrically connects theanode and the cathode, the conductive connector including an alloyincluding Cu and Zn. The galvanic phosphorus removal stage also includesseparating the salt including the phosphorus from the treated water. Thewater produced by the method has a lower phosphorus concentration and alower nitrogen concentration than the starting material water. The waterproduced by the method has a total phosphorus concentration of about0.0001 ppm to 0.05 ppm, and a total nitrogen concentration of about 0ppm to about 1 ppm.

In various embodiments, the present invention provides a method ofremoving nitrogen from water. The method includes passing the waterthrough an electrolytic cell to remove nitrogen from the water asnitrogen gas.

In various embodiments, the present invention provides a method ofremoving nitrogen from water. The method includes passing the waterthrough an electrolytic cell to remove nitrogen from the water asnitrogen gas. The electrolytic cell includes a cathode includingstainless steel and an anode including titanium oxide, ruthenium oxide,and iridium oxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti); or titaniumoxide and ruthenium oxide supported on titanium (TiO₂—RuO₂/Ti); ortitanium and platinum (Ti—Pt); or a combination thereof. The removal ofnitrogen as nitrogen gas removes 80-100% of ammonia from the water.

In various embodiments, the present invention provides a system forremoval of nitrogen and phosphorus from water. The system includes anelevated pH phosphorus removal stage configured to raise pH of startingmaterial water to greater than or equal to 7.5 to precipitate aphosphorus salt from the water and configured to remove the precipitatedphosphorus salt from the water. The system includes an electrolyticnitrogen removal stage including an electrolytic cell configured toremove nitrogen from the water as nitrogen gas. The system includes agalvanic phosphorus removal stage including a galvanic cell including ananode including Mg, Al, Fe, Zn, or a combination thereof, and a cathodehaving a different composition than the anode, the cathode including Cu,Ni, Fe, or a combination thereof, the galvanic cell configured to form atreated water including a salt that includes phosphorus from the water,wherein the galvanic phosphorus removal stage is configured to separatethe salt including the phosphorus from the treated water. The waterproduced by the system has a lower phosphorus concentration and a lowernitrogen concentration than the starting material water.

In various embodiments, the present invention provides an apparatus forremoval of nitrogen from water. The apparatus includes an electrolyticcell through which water is configured to be flowed to remove nitrogenfrom the water as nitrogen gas. The electrolytic cell includes a cathodeincludes stainless steel and/or titanium and an anode comprisingtitanium oxide, ruthenium oxide, and iridium oxide supported on titanium(TiO₂—RuO₂—IrO₂/Ti); or titanium oxide and ruthenium oxide supported ontitanium (TiO₂—RuO₂/Ti); or titanium and platinum (Ti—Pt); or acombination thereof. The removal of nitrogen as nitrogen gas removes80-100% of ammonia from the water.

In various embodiments, the method of phosphorus and/or nitrogen removalof the present invention has certain advantages over other methods ofremoval phosphorus from water. For example, in some embodiments, themethod of phosphorus and/and nitrogen removal of the present inventioncan remove a larger amount of phosphorus and/or nitrogen, accomplish alower concentration of phosphorus and/or nitrogen, achieve phosphorusand/or nitrogen removal with greater efficiency or less cost, utilize asmaller footprint, or a combination thereof, as compared to othermethods.

In various embodiments, the method of phosphorus and/or nitrogen removalof the present invention can be performed with less oxidation ofincoming water as compared to other methods, or with no oxidation ofincoming water. In some embodiments that include a galvanic cellincluding an anode that includes Al, a higher pH near that anode fromproduction of hydroxide ions can induce or enhance precipitation of thealuminum salt (e.g., AlPO₄, aluminum hydroxide, or a combinationthereof). In some embodiments, the ratio of Al to P used to remove thephosphorus from the water is lower than those reported by other methods,such as methods using an addition of an aluminum salt.

BRIEF DESCRIPTION OF THE FIGURES

The drawings illustrate generally, by way of example, but not by way oflimitation, various embodiments of the present invention.

FIG. 1A illustrates an electrochemical cell view from a major face, inaccordance with various embodiments.

FIG. 1B illustrates a zoomed-in cutaway edge view of an electrochemicalcell, according to various embodiments.

FIG. 2A illustrates a photograph along the edge of an Al—Cuelectrochemical cell, in accordance with various embodiments.

FIG. 2B illustrates a photograph along an edge of a plurality of Al—Cuelectrochemical cells, in accordance with various embodiments.

FIG. 2C illustrates a photograph of a major face of a Mg—Cuelectrochemical cell, in accordance with various embodiments.

FIG. 2D illustrates a photograph of an edge of a Mg—Cu electrochemicalcell, in accordance with various embodiments.

FIG. 2E illustrates a photograph of an edge of a Mg—Cu electrochemicalcell, in accordance with various embodiments.

FIG. 2F illustrates a photograph showing a top view of a system forremoving materials from water, in accordance with various embodiments.

FIG. 2G illustrates a photograph showing a side-view of a system forremoving materials from water, in accordance with various embodiments.

FIG. 3 illustrates electrical current generated by an Al—Cu cell versustime for solutions having various conductivities, in accordance withvarious embodiments.

FIG. 4 illustrates electrical current generated by an Al—Cu cell versustime for solutions having various pH levels, in accordance with variousembodiments.

FIG. 5A illustrates electrical current generated by an Mg—Cu cell versustime for solutions having various conductivities, in accordance withvarious embodiments.

FIG. 5B illustrates electrical current generated by an Mg—Cu cell versustime for solutions having various pH levels, in accordance with variousembodiments.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Throughout this document, values expressed in a range format should beinterpreted in a flexible manner to include not only the numericalvalues explicitly recited as the limits of the range, but also toinclude all the individual numerical values or sub-ranges encompassedwithin that range as if each numerical value and sub-range is explicitlyrecited. For example, a range of “about 0.1% to about 5%” or “about 0.1%to 5%” should be interpreted to include not just about 0.1% to about 5%,but also the individual values (e.g., 1%, 2%, 3%, and 4%) and thesub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within theindicated range. The statement “about X to Y” has the same meaning as“about X to about Y,” unless indicated otherwise. Likewise, thestatement “about X, Y, or about Z” has the same meaning as “about X,about Y, or about Z,” unless indicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.The statement “at least one of A and B” or “at least one of A or B” hasthe same meaning as “A, B, or A and B.” In addition, it is to beunderstood that the phraseology or terminology employed herein, and nototherwise defined, is for the purpose of description only and not oflimitation. Any use of section headings is intended to aid reading ofthe document and is not to be interpreted as limiting; information thatis relevant to a section heading may occur within or outside of thatparticular section.

In the methods described herein, the acts can be carried out in anyorder without departing from the principles of the invention, exceptwhen a temporal or operational sequence is explicitly recited.Furthermore, specified acts can be carried out concurrently unlessexplicit claim language recites that they be carried out separately. Forexample, a claimed act of doing X and a claimed act of doing Y can beconducted simultaneously within a single operation, and the resultingprocess will fall within the literal scope of the claimed process.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range, and includes the exactstated value or range. The term “substantially” as used herein refers toa majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%,95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999%or more, or 100%. The term “substantially free of” as used herein canmean having none or having a trivial amount of, such that the amount ofmaterial present does not affect the material properties of thecomposition including the material, such that about 0 wt % to about 5 wt% of the composition is the material, or about 0 wt % to about 1 wt %,or about 5 wt % or less, or less than or equal to about 4.5 wt %, 4,3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1,0.01, or about 0.001 wt % or less, or about 0 wt %.

In various embodiments, salts having a positively charged counterion caninclude any suitable positively charged counterion. For example, thecounterion can be ammonium (NH₄ ⁺), or an alkali metal such as sodium(Na⁺), potassium (K⁺), or lithium (Li⁺). In some embodiments, thecounterion can have a positive charge greater than +1, which can in someembodiments complex to multiple ionized groups, such as Zn²⁺, Al³⁺, oralkaline earth metals such as Ca²⁺ or Mg²⁺.

All concentrations of phosphorus, nitrogen, chloride, ammonia,magnesium, and aluminum referred to are dissolved concentrations ofthese materials in elemental or non-elemental (e.g., as a compound orion including the material) forms, unless otherwise indicated. Allconcentrations given herein are by weight unless otherwise indicated.

As used herein, “total phosphorus concentration” refers to theconcentration of all forms of phosphorus, as measured by US-EPA 365.1:Determination of Phosphorus by Semi-Automated Colorimetry or equivalent,unless otherwise indicated.

As used herein, “dissolved phosphorus concentration” refers to theconcentration of all forms of phosphorus passable though a 0.45 micronfilter and as measured by US-EPA 365.1: Determination of Phosphorus bySemi-Automated Colorimetry or equivalent, unless otherwise indicated.

As used herein, “reactive phosphorus concentration” refers to thesoluble reactive phosphorus in solution (e.g., orthophosphate) asmeasured by US-EPA 365.1: Determination of Phosphorus by Semi-AutomatedColorimetry or equivalent unless otherwise indicated.

Method of Removing Phosphorus and Nitrogen from Water.

Various embodiments of the present invention provide a method ofremoving phosphorus and nitrogen from water. The method can includepassing starting material water including nitrogen and phosphorusthrough an elevated pH phosphorus removal stage. The elevated pHphosphorus removal stage can include raising pH of the water to greaterthan or equal to 7.5 to precipitate a phosphorus salt from the water,and removing the precipitated phosphorus salt from the water. The methodcan include passing the water through an electrolytic nitrogen removalstage that includes passing the water through an electrolytic cell toremove nitrogen from the water as nitrogen gas. The method can alsoinclude passing the water through a galvanic phosphorus removal stagethat includes immersing a galvanic cell in the water to form treatedwater including a salt that includes phosphorus from the water. Thegalvanic cell can include an anode including Mg, Al, Fe, Zn, or acombination thereof, and a cathode having a different composition thanthe anode, the cathode including Cu, Ni, Fe, or a combination thereof.The galvanic phosphorus removal stage can include separating the saltincluding the phosphorus from the treated water. The water produced bythe method can have a lower phosphorus concentration and a lowernitrogen concentration than the starting material water (e.g., lowerdissolved phosphorus/nitrogen concentration).

The water can flow from the elevated pH phosphorus removal stage to theelectrolytic nitrogen removal stage. The water can flow from theelectrolytic nitrogen removal stage to the galvanic phosphorus removalstage. The water produced by the galvanic phosphorus removal stage canbe the final water product of the method, or the water can flow from thegalvanic phosphorus removal stage to an optional further removal ofnitrogen stage. The method can optionally include one or moreintervening steps between any one or more stages; in some embodiments,the method includes one or more intervening steps, while in otherembodiments, the method is substantially free of intervening stepsbetween the elevated pH phosphorus removal stage and the electrolyticnitrogen removal stage, between the electrolytic nitrogen removal stageand the galvanic phosphorus removal stage, between the galvanicphosphorus removal stage and the optional further removal of nitrogenstage, or a combination thereof.

The starting material water can be taken from any suitable source, suchas a natural source of water in the environment, drinking water (e.g.,for removal of struvite to prevent formation in pipes), industrialwaste-water, industrial cooling water, or a combination thereof. Thewater can be water taken from a source including a natural source ofwater in the environment, such as a pond, lake, river, stream, and thelike. In some embodiments, the method can include taking the water fromthe source, returning the water to the source after removal of nitrogenand phosphorus, or a combination thereof. The starting material watercan be a product of fertilizer production or mining. For example, thestarting material water can be water taken from a phosphate minereservoir, such as water originated from a process of dissolvingphosphate-containing rock to produce phosphoric acid.

The starting material water can have any suitable pH, such as a pH ofless than 7.5, or 1 to less than 7.5, or 2-6, 4-5, or 1 or more but lessthan 7.5, or less than, equal to, or greater than 1.5, 2, 2.5, 3, 3.5,4, 4.5, 5, 5.5, 6, 6.5, 7, or 7.5 or less.

The phosphorus in the starting material water can be in any suitableform, such as elemental phosphorus, inorganic phosphorus, organicphosphorus, a dissolved form of phosphorus, a solid form of phosphorus,oxidized phosphorus, or a combination thereof.

The nitrogen in the water can be in any suitable form, such as in theform of elemental nitrogen, inorganic nitrogen, organic nitrogen, adissolved form of nitrogen, a solid form of nitrogen, oxidized nitrogen,or a combination thereof.

The starting material water can have any suitable ammonia concentration,such as 50 ppm to 5,000 ppm, 150 ppm to 400 ppm, or 50 ppm or more, orless than, equal to, or greater than 100 ppm, 150, 200, 250, 300, 350,400, 450, 500, 600, 750, 1,000, 2,000, 3,000, 4,000, or 5,000 ppm orless.

The starting material water can have any suitable reactive phosphorusconcentration, such as 10 ppm to 10,000 ppm, 50 ppm to 400 ppm, or 10ppm or more, or less than, equal to, or greater than 25 ppm, 50, 100,150, 200, 250, 300, 350, 400, 500, 750, 1,000, 2,000, 4,000, 6,000,8,000, or 10,000 ppm or less.

The starting material water can have any suitable sodium concentration,such as 50 ppm to 20,000 ppm, 400 ppm to 5,000 ppm, or 50 ppm or more,or less than, equal to, or greater than 100 ppm, 200, 400, 600, 800,1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 7,500,10,000, 12,500, 15,000, 17,500, or 20,000 ppm or less.

The starting material water can have any suitable magnesiumconcentration, such as 10 ppm to 10,000 ppm, 50 ppm to 600 ppm, or 10ppm or more, or less than, equal to, or greater than 50 ppm, 100, 200,300, 400, 500, 600, 700, 800, 1,000, 2,000, 4,000, 6,000, 8,000, or10,000 ppm or less.

The starting material water can have any suitable chlorideconcentration, such as 50 ppm to 40,000 ppm, 200 ppm to 10,000 ppm, or50 ppm or more, or less than, equal to, or greater than 100 ppm, 200,500, 1,000, 2,000, 4,000, 6,000, 8,000, 10,000, 15,000, 20,000, 30,000,or 40,000 ppm or less.

The water produced by the method can have a total phosphorusconcentration, a dissolved phosphorus concentration, a reactivephosphorus concentration, or a combination thereof, of about 0 ppm toabout 1 ppm, about 0.0001 ppm to 0.1 ppm, about 0.0001 ppm to 0.05 ppm,or about 0 ppm, or less than, equal to, or greater than about 0.0001ppm, 0.0002, 0.0004, 0.0006, 0.0008, 0.0010, 0.0012, 0.0014, 0.0016,0.0018, 0.0020, 0.0022, 0.0024, 0.0026, 0.0028, 0.0030, 0.0032, 0.0034,0.0036, 0.0038, 0.0040, 0.0045, 0.0050, 0.0060, 0.0080, 0.01, 0.02,0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, or about 1.0 ppm or more. Thewater produced by the method can have a total phosphorus concentration,a dissolved phosphorus concentration, a reactive phosphorusconcentration, or a combination thereof, that is about 0% to 70% of therespective total phosphorus concentration, a dissolved phosphorusconcentration, a reactive phosphorus concentration, or a combinationthereof, of the starting material water, or about 0% to about 20%, orabout 0%, or less than, equal to, or greater than about 0.001%, 0.005,0.01, 0.05, 0.1, 0.5, 1, 2, 4, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50,55, 60, 65, or about 70% or more.

The water produced by the method can have any suitable total nitrogenconcentration, dissolved nitrogen concentration, or a combinationthereof, such as 0 ppm to about 2 ppm, 0 ppm to about 1 ppm, or about 0ppm, or less than, equal to, or greater than 0.001 ppm, 0.0012, 0.0014,0.0016, 0.0018, 0.0020, 0.0022, 0.0024, 0.0026, 0.0028, 0.0030, 0.0032,0.0034, 0.0036, 0.0038, 0.0040, 0.0045, 0.0050, 0.0060, 0.0080, 0.01,0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.1, 1.2, 1.4, 1.6,1.8, or about 2 ppm or less. The water produced by the method can have atotal nitrogen concentration, a dissolved nitrogen concentration, or acombination thereof, that is about 0% to about 70% of the respectivetotal nitrogen concentration, dissolved nitrogen concentration, or acombination thereof, of the starting material water, or about 0% toabout 30%, or about 0%, or less than, equal to, or greater than about0.001%, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 4, 6, 8, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, or about 70% or more.

Elevated pH Phosphorus Removal Stage.

The method of removing phosphorus and nitrogen can include passing thewater through an elevated pH phosphorus removal stage. The elevated pHphosphorus removal stage The elevated pH phosphorus removal stage caninclude raising pH of the water to greater than or equal to 7.5 toprecipitate a phosphorus salt from the water, and removing theprecipitated phosphorus salt from the water.

Raising the pH of the water to precipitate the phosphorus salt from thewater can include raising the pH of the water to any suitable level toinduce a suitable amount of precipitation of the phosphorus salt tooccur. Raising the pH of the water to precipitate the phosphorus saltcan include raising the pH of the water to 7.5 to 12, 8.5 to 9.5, or 7.5or more, or less than, equal to, or greater than 8, 8.5, 9, 9.5, 10,10.5, 11, 11.5, or 12 or less. Raising the pH of the water toprecipitate the phosphorus salt from the water can include adding one ormore bases to the water, such as any suitable one or more bases, such asNaOH, KOH, or a combination thereof. In various aspects, the methodincludes adding NaOH to the water, such as 5% aqueous NaOH.

The precipitation can occur without aid of other materials, or theprecipitation can occur in the presence of one or more addedflocculants. The flocculant can be any suitable flocculant, such as ananionic, cationic, or nonionic flocculant, a metal salt coagulant, astarch-based flocculant, or a combination thereof. The flocculant can bean anionic polymer flocculant.

The removal of the precipitated phosphorus salt can be performed in anysuitable way such that the precipitate is separated from the water.Removing the precipitated phosphorus salt from the water can includedecantation, settling, filtration, or a combination thereof.

The precipitated phosphorus salt can include any suitable one or morephosphorus salts. The composition of the one or more precipitatedphosphorus salts can depend on the composition of the starting materialwater. The precipitated phosphorus salt can include struvite, calciumphosphate, or a combination thereof.

The elevated pH phosphorus removal stage can remove any suitable amountof phosphorus from the water. For example, the elevated pH phosphorusremoval stage can remove 70-100% of the reactive phosphorus in thewater, 90-98%, or 70% or more, or less than, equal to, or greater than72%, 74, 76, 78, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, 99.9, or 99.99% or less.

The elevated phosphorus removal stage can optionally remove ammonia fromthe water. The elevated phosphorus removal stage can remove any suitableamount of ammonia from the water, such as 0-60%, 20-30%, or 0%, or lessthan, equal to, or greater than 10%, 20, 25, 30, 35, 40, 45, 50, 55, or60% or less.

Electrolytic Nitrogen Removal Stage.

The method of removing phosphorus and nitrogen can include passing thewater through an electrolytic nitrogen removal stage that includespassing the water through an electrolytic cell to remove nitrogen fromthe water as nitrogen gas.

The electrolytic nitrogen removal stage can include passing the waterthrough one electrolytic cell or multiple electrolytic cells. Passingthe water through the electrolytic cell can include allowing the waterto contact the anode and the cathode and can include allowing the waterto pass between the anode and the cathode. The electrolytic cell can bepartially or fully submerged/immersed in the water. Shear can be appliedto the water as it is passed through the electrolytic cell, to increaseexposure of the water to the cathode and anode surfaces.

Prior to passing through the electrolytic cell, the water can have anysuitable chloride concentration, such as 50 ppm to 40,000 ppm, 200 ppmto 10,000 ppm, or or 50 ppm or more, or less than, equal to, or greaterthan 100 ppm, 200, 500, 1,000, 2,000, 4,000, 6,000, 8,000, 10,000,15,000, 20,000, 30,000, or 40,000 ppm or less.

The water immersing the electrolytic cell can have any suitable pH, suchas a pH of 6 to 12, 6 to 7, or 6 or more, or less than, equal to, orgreater than 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12 orless. The method can include adding one or more bases to the water toregulate or maintain the pH of the water, such as sodium hydroxide; inother embodiments, the method is free of adding acids or bases to thewater to maintain or regulate the pH thereof.

The electrolytic cell can be operated in any suitable way to removenitrogen as nitrogen gas from the water. The cell can be operated withDC current or AC current. The electrolytic cell can be operated with anysuitable current density, such as 0.001-0.1 A/cm², 0.02-0.04 A/cm², or0.001 A/cm² or more, or less than, equal to, or greater than 0.005,0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06, 0.07,0.08, 0.09, or 0.1 A/cm² or less.

The electrolytic cell includes an anode. The anode can include titaniumoxide, ruthenium oxide, and iridium oxide supported on titanium(TiO₂—RuO₂—IrO₂/Ti); or titanium oxide and ruthenium oxide supported ontitanium (TiO₂—RuO₂/Ti); or titanium and platinum (Ti—Pt); or acombination thereof. The anode and cathode materials can be selectedsuch that the electrodes favor the formation of chlorine gas to formhypochlorite during operation of the electrolytic cell.

The electrolytic cell includes a cathode. The cathode can includetitanium, stainless steel, or a combination thereof. The cathode caninclude stainless steel.

The electrolytic cell can include a spacing between the anode andcathode, such as a spacing of 0.5-8 mm, 2-4 mm, or 0.5 mm or more, orless than, equal to, or greater than 1 mm, 1.5, 2, 2.5, 3, 3.5, 4, 4.5,5, 6, 7, or 8 mm or less.

The method is not limited to any particular mechanism of removingnitrogen from the water as ammonia using the electrolytic cell. Theremoving of nitrogen as nitrogen gas can include converting ammonia inthe water to nitrogen gas using the electrolytic cell. Passing the waterthrough the electrolytic nitrogen removal stage can produce hypochloritein the water which can react with ammonia in the water to form thenitrogen gas, which can be released to the environment. The reaction cantake place via NH₄ ⁺+1.5 HOCl→0.5 N₂,+1.5H₂O+2.5H⁺+1.5 Cl⁻. Theelectrolytic cell can produce any suitable hypochlorite concentration inthe water being passed therethrough, such as 100-20,000 ppmhypochlorite, 2000-2500 ppm, or 100 ppm or more, or less than, equal to,or greater than 200 ppm, 400, 600, 800, 1,000, 1,200, 1,400, 1,600,1,800, 2,000, 2,100, 2,200, 2,300, 2,400, 2,500, 2,600, 2,800, 3,000,4,000, 6,000, 8,000, 10,000, 15,000, or 20,000 ppm or less.

The electrolytic nitrogen removal stage can remove any suitable amountof nitrogen from the water. For example, passing the water through theelectrolytic nitrogen removal stage can remove 80% to 100% of ammoniafrom the water, 99-100%, or 80% or more, or less than, equal to, orgreater than 81%, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94,95, 96, 97, 98, 99, 99.9, 99.99, or 99.999% or less.

In various embodiments, the electrolytic nitrogen removal stage can alsoinclude removing phosphorus from the water, such as any suitable amountof phosphorus. For example, passing the water through the electrolyticnitrogen removal stage can remove 0.1 to 90% of reactive phosphorus fromthe water, or 1-30%, or 0.1% or more, or less than, equal to, or greaterthan 2%, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 40, 50,60, 70, 80, or 90% or less.

Galvanic Phosphorus Removal Stage.

The method of removing nitrogen and phosphorus can also include passingthe water through a galvanic phosphorus removal stage that includesimmersing a galvanic cell in the water to form treated water including asalt that includes phosphorus from the water. The galvanic cell caninclude an anode including Mg, Al, Fe, Zn, or a combination thereof, anda cathode having a different composition than the anode, the cathodeincluding Cu, Ni, Fe, or a combination thereof. The galvanic phosphorusremoval stage can include separating the salt including the phosphorusfrom the treated water. The galvanic phosphorus removal stage is free ofapplying electrical potential (e.g., applied potential from a sourceexternal to the galvanic cell) across the anode and the cathode of thegalvanic cell.

The galvanic phosphorus removal stage can reduce total phosphorusconcentration of the water, dissolved phosphorus concentration of thewater, reactive phosphorus concentration of the water, total nitrogenconcentration of the water, a dissolved nitrogen concentration of thewater, or a combination thereof, by any suitable amount, such as 70% to100%, 80% to 100%, 90% to 100%, or 70% or more, or less than, equal to,or greater than 71%, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84,85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99,or 99.999% or less.

The water can have a total phosphorus concentration, a dissolvedphosphorus concentration, a reactive phosphorus concentration, or acombination thereof, of about 0.001 ppm to about 10,000 ppm, about 0.01ppm to about 20 ppm, or about 0.001 ppm or less, or less than, equal to,or greater than about 0.005 ppm, 0.01, 0.02, 0.04, 0.06, 0.08, 0.1,0.15, 0.2, 0.4, 0.6, 0.8, 1, 2, 4, 6, 8, 10, 15, 20, 40, 60, 80, 100,150, 200, 400, 600, 800, 1,000, 1,500, 2,000, 4,000, 6,000, 8,000, orabout 10,000 ppm or more.

The water having the salt including the phosphorus separated therefromcan have a total phosphorus concentration, a dissolved phosphorusconcentration, a reactive phosphorus concentration, or a combinationthereof, of about 0 ppm to about 1 ppm, about 0.0001 ppm to 0.1 ppm,about 0.0001 ppm to 0.05 ppm, or about 0 ppm, or less than, equal to, orgreater than about 0.0001 ppm, 0.0002, 0.0004, 0.0006, 0.0008, 0.0010,0.0012, 0.0014, 0.0016, 0.0018, 0.0020, 0.0022, 0.0024, 0.0026, 0.0028,0.0030, 0.0032, 0.0034, 0.0036, 0.0038, 0.0040, 0.0045, 0.0050, 0.0060,0.0080, 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, or about1.0 ppm or more. The water having the salt including the phosphorusseparated therefrom can have a total phosphorus concentration, adissolved phosphorus concentration, a reactive phosphorus concentration,or a combination thereof, that is about 0% to 70% of the respectivetotal phosphorus concentration, a dissolved phosphorus concentration, areactive phosphorus concentration, or a combination thereof, of thewater that is initially contacted with the galvanic cell, or about 0% toabout 20%, or about 0%, or less than, equal to, or greater than about0.001%, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 4, 6, 8, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, or about 70% or more.

During the immersing of the galvanic cell in the water, the water canhave any suitable pH. The pH can be about 2 to about 14, about 5 toabout 11, about 5 to about 7, about 10 to about 11, or less then, equalto, or greater than about 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9,7, 7.5, 8, 8.5, 9, 9.5, 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7,10.8, 10.9, 11, 11.5, 12, 12.5, 13, 13.5, or about 14 or more.

The galvanic phosphorus removal stage can include adding acid, base, ora combination thereof to the water to adjust or control the pH thereof.In some embodiments, the method is free of adding acid, base, or acombination thereof to the water. The acid, base, or combination thereofcan be added to the water before the immersing of the galvanic cell inthe water, during the immersing of the galvanic cell in the water, afterthe immersing of the galvanic cell in the water, or a combinationthereof.

The galvanic phosphorus removal stage can include recirculating thewater that immerses the galvanic cell to contact the water with thegalvanic cell multiple times. The water can optionally be filteredduring the recirculation, such as to remove salt including phosphorusfrom the water.

Immersing a galvanic cell in water can form treated water including asalt that includes the phosphorus. Contact between the water and thegalvanic cell can cause formation of the salt that includes thephosphorus. At least some of the salt including the phosphorus in thetreated water can include a solid. Formation of the solid including thephosphorus can include precipitation, flocculation, or a combinationthereof.

Separating the salt including the phosphorus from the treated water canbe performed in any suitable way. The separating can includedecantation, settling, filtration, or a combination thereof. Theseparating can include separating the treated water from the galvaniccell (e.g., removing water immersing the cell that has been filtered orfrom which the salt including the phosphorus has otherwise beenseparated). The separation can occur during a recirculation of the waterback to the galvanic cell. The separation can be performed during thecontacting the galvanic cell with the water, such as via a filter thatis immersed in the water and is continuously filtering the water duringthe contacting. The separation can occur after the water is removed fromthe water that immerses the galvanic cell, such as via a filter on anexit line out of the system. The filtration can be conducted using aglass frit, a fabric filter, a paper filter, a disk filter, a rotaryfilter, a drum filter, a screen, a sieve, particulate filtration media,a filter aid, or a combination thereof. The separated water can beoptionally further treated, such as via further contact with the same ordifferent galvanic cell, filtration, treatment to remove one or moreother non-phosphorus materials, pH adjusted, or a combination thereof.

The anode can be a sacrificial anode that is consumed during treatmentof the water. The salt including the phosphorus that is formed uponcontact of the water with the galvanic cell can include a material fromthe anode. The method can include forming a hydroxide salt including amaterial from the anode during the immersing of the galvanic cell in thewater. Separating the salt including the phosphorus from the treatedwater can further include separating the hydroxide salt including thematerial from the anode from the treated water.

The method can include forming H₂ and HO⁻ at the anode (e.g., generateon the surface of the anode, from water) during the immersing of thegalvanic cell in the water. The method can include forming H₂ and HO⁻ atthe cathode (e.g., generate on the surface of the cathode, from water)during the immersing of the galvanic cell in the water. The method caninclude forming H₂O₂, HO₂ ⁻, or a combination thereof at the cathode(e.g., generate on the surface of the cathode) during the immersing ofthe galvanic cell in the water. The method can include applying shear tothe water during the immersing of the galvanic cell in the water. Theshear can be sufficient to dislodge at least some bubbles (e.g.,including H₂) from the surface of the anode, cathode, or a combinationthereof. The shear can be sufficient to at least partially prevent orreduce oxide formation at the surface of the anode. The method caninclude applying a mechanical force to the galvanic cell immersed in thewater, such as a rapping, knocking, agitating, vibration, ultrasound,and the like. The mechanical force can be sufficient to dislodge atleast some bubbles including H₂ from the surface of the anode, cathode,or a combination thereof; at least partially prevent oxide formation atthe surface of the anode; at least partially prevent agglomeration ofthe salt including the phosphorus on the surface of the anode; or acombination thereof.

The separated water can have a total nitrogen concentration, a dissolvednitrogen concentration, or a combination thereof, that is about 0% toabout 70% of the respective total nitrogen concentration, dissolvednitrogen concentration, or a combination thereof, of the water, or about0% to about 30%, or about 0%, or less than, equal to, or greater thanabout 0.001%, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 4, 6, 8, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, or about 70% or more.

The method can further include forming NH₃, NH₄ ⁺, or a combinationthereof, at the cathode (e.g., at the surface of the cathode), whereinthe NH₃ and NH₄ ⁺ include the nitrogen from the water. The method caninclude forming a salt including the nitrogen during the immersing ofthe galvanic cell in the water. The separating of the salt including thephosphorus from the treated water can include separating the saltincluding the nitrogen from the treated water. The salt including thenitrogen can include NH₄MgPO₄ or a hydrate thereof (e.g., struvite).

The cathode of the galvanic cell can include Cu, Ni, Fe, or acombination thereof, such as Cu or a Cu alloy. The cathode can be asolid material that is predominantly Cu, Ni, Fe, alloys thereof, or acombination thereof, or another material that is coated withpredominantly Cu, Ni, Fe, alloys thereof, or a combination thereof. Thecathode can be substantially free of materials other than Cu, Ni, Fe,alloys thereof, or a combination thereof. The cathode can be about 50 wt% to about 100 wt % Cu, Ni, Fe, alloys thereof, or a combinationthereof, about 90 wt % to about 100 wt %, or less than, equal to, orgreater than about 50 wt %, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90,91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.9, 99.99, or about 99.999wt % or more. In some embodiments, the cathode includes Cu and the anodeincludes Mg. In some embodiments, the cathode includes Cu and the anodeincludes Al.

The anode can be a solid material of approximately homogeneouscomposition or can be a coating on another material. The anode has adifferent composition than the cathode. The anode can include Mg, Al,Fe, Zn, or a combination thereof. The anode can include an alloy thatincludes Mg, Al, Fe, Zn, or an alloy thereof. The Mg, Al, Fe, Zn, alloysthereof, or combinations thereof, can be about 50 wt % to about 100 wt %of the anode, or less than, equal to, or greater than about 50 wt %, 55,60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or about 99,99.5, 99.9, 99.99, or about 99.999 wt % or more. The anode can besubstantially free of materials other than Mg, Al, Fe, Zn, alloysthereof, or combinations thereof.

The anode can further include Ag, Pt, Au, or a combination thereof. TheAg, Pt, Au, or the combination thereof is about 0.0001 wt % to about 20wt %, about 0.0001 wt % to about 5 wt %, or about 0 wt %, or about0.0001 wt % or less, or 0.0002, 0.0004, 0.0006, 0.0008, 0.0010, 0.0012,0.0014, 0.0016, 0.0018, 0.0020, 0.0022, 0.0024, 0.0026, 0.0028, 0.0030,0.0032, 0.0034, 0.0036, 0.0038, 0.0040, 0.0045, 0.0050, 0.0060, 0.0080,0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.5, 2, 4, 6,8, 10, 12, 14, 16, 18, or about 20 wt % or more.

The anode can include Mg or an Mg alloy. The anode can be substantiallyfree of materials other than Mg or alloys thereof. The anode can bemagnesium alloy AZ91 that is about 90 wt % Mg, about 9 wt % Al, andabout 1 wt % Zn. The anode can be about 50 wt % to about 100 wt % Mg orMg alloy, about 90 wt % to about 100 wt % Mg or Mg alloy, or less than,equal to, or greater than about 50 wt %, 55, 60, 65, 70, 75, 80, 85, 90,91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.9, 99.99, or about 99.999wt % Mg or Mg alloy or more. The salt including the phosphorus caninclude magnesium phosphate, magnesium potassium phosphate (e.g.,“K-struvite”), a hydrate thereof, or a combination thereof, wherein themagnesium phosphate or magnesium potassium phosphate includes Mg fromthe anode. The magnesium phosphate can be in any suitable form, such asmonomagnesium phosphate (Mg(H₂PO₄)₂), dimagnesium phosphate (MgHPO₄),trimagnesium phosphate (Mg₃(PO₄)₂), a hydrate thereof, or a combinationthereof. The separating of the salt including the phosphorus from thetreated water can include separating the magnesium phosphate from thetreated water. The water can further includes nitrogen, wherein the saltincluding the phosphorus includes NH₄MgPO₄ or a hydrate thereof (e.g.,struvite), with the NH₄MgPO₄ including the phosphorus and Mg from theanode. The method can include forming Mg(OH)₂ including Mg from theanode during the immersing of the galvanic cell in the water. Theseparating of the salt including the phosphorus from the treated watercan include separating the Mg(OH)₂ from the treated water. During theimmersing of the galvanic cell in the water, the water can have a pH ofabout 9.5 to about 11.5, or about 10 to about 11, or less than, equalto, or greater than 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3,10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, orabout 11.5 or more. The method can include regulating a rate ofintroduction of fresh water to the galvanic cell such that the waterthat immerses the galvanic cell is maintaining at a pH of about 9.5 toabout 11.5, or about 10 to about 11, or less than, equal to, or greaterthan 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6,10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, or about 11.5 or more.The method can include immersing the galvanic cell in the water untilthe water reaches a pH of about 9.5 to about 11.5 or about 10 to about11, and then regulating a rate of introduction of fresh water to thegalvanic cell such that the water that immerses the galvanic cell ismaintained at a pH of about 9.5 to about 11.5 or about 10 to about 11.

The anode can include Al. The anode can be substantially free ofmaterials other than Al. The anode can be about 50 wt % to about 100 wt% Al, about 90 wt % to about 100 wt % Al, or less than, equal to, orgreater than about 50 wt %, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93,94, 95, 96, 97, 98, or about 99, 99.5, 99.9, 99.99, or about 99.999 wt %or more. The salt including phosphorus can include A1PO4 or a hydratethereof. Separating of the salt including the phosphorus from thetreated water can include separating the AlPO₄ from the treated water.The method can include forming aluminum hydroxide or a hydrate thereof(e.g., Al(OH)₃ or polyaluminum hydroxide), the aluminum hydroxideincluding Al from the anode during the immersing of the galvanic cell inthe water. Separating of the salt including the phosphorus from thetreated water can include separating the aluminum hydroxide from thetreated water. During the immersing of the galvanic cell in the water,the water has a pH of about 4 to about 8, about 5 to about 7, or about 4or less, or about 4.2, 4.4, 4.6, 4.8, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6,5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.2,7.4, 7.6, 7.8, or about 8 or more. The method can include regulating arate of introduction of an acid to the water such that the water thatimmerses the galvanic cell is maintained at a pH of about 4 to about 8,about 5 to about 7, or about 4 or less, or about 4.2, 4.4, 4.6, 4.8, 5,5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4,6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.2, 7.4, 7.6, 7.8, or about 8 or more. Theacid can be added to the water prior to the immersion of the galvaniccell in the water, during the immersion of the galvanic cell in thewater, after the immersion of the galvanic cell in the water, or acombination thereof. The acid can be any suitable acid, at any suitableconcentration. The acid can include sulfuric acid, acetic acid,hydrochloric acid, or a combination thereof. The method can includeflocculating salts that include Al from the treated water.

The cathode can have a work function that is larger than the workfunction of the anode. For example, Cu has a work function of about4.53-5.10 eV, Mg has a work function of about 3.66 eV, and Al has a workfunction of about 4.06-4.26 eV. The conductive connector can have a workfunction that is between the work function of the cathode and the workfunction of the cathode.

The galvanic cell can include a conductive connector that electricallyconnects the anode and the cathode. The conductive connector has adifferent composition than the anode or the cathode. The conductiveconnector can be a solid material with a homogeneous composition or canbe a coating on another material. The conductive connector can includeCu, Zn, Fe, Cd, Ni, Sn, Pb, or a combination thereof. The conductiveconnector can include Cu. The conductive connector can include Zn. Theconductive connector can include an alloy including Cu and Zn. Theconductive connector can include brass. The conductive connector caninclude brass, and can be substantially free of other materials. Theconductive connector can be about 50 wt % to about 100 wt % brass, about90 wt % to about 100 wt %, or less than, equal to, or greater than about50 wt %, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98,or about 99, 99.5, 99.9, 99.99, or about 99.999 wt % or more.

The water can have any suitable conductivity during immersion of thegalvanic cell in the water, such as about 100 μS to about 1,000,000 μS,or about 300 μS to about 100,000 μS, or about 100 μS to about 1,200 μS,or less than, equal to, or greater than about 100 μS, 200, 300, 400,500, 600, 700, 800, 900, 1,000, 1,100, 1,200, 1,500, 2,000, 4,000,6,000, 10,000, 15,000, 20,000, 50,000, 100,000, 150,000, 200,000,250,000, 500,000, 750,000, or about 1,000,000 μS or more . The methodcan be free of regulation of the conductivity of the water. In someembodiments, the method can include regulating the conductivity of thewater such that the conductivity is maintained at about 100 μS to about1,000,000 μS, or about 300 μS to about 100,000 μS, or about 100 μS toabout 1,200 μS, or less than, equal to, or greater than about 100 μS,200, 300, 400, 500, 600, 700, 800, 900, 1,000, 1,100, 1,200, 1,500,2,000, 4,000, 6,000, 10,000, 15,000, 20,000, 50,000, 100,000, 150,000,200,000, 250,000, 500,000, 750,000, or about 1,000,000 μS or more.Regulating the conductivity of the water can include regulating a rateof introduction of fresh water to the galvanic cell. Regulating theconductivity of the water can include adding one or more salts to thewater. The salt can be added to the water before immersing the galvaniccell in the water, during the immersion of the galvanic cell in thewater, after the immersion of the galvanic cell in the water, or acombination thereof. The one or more salts added to the water toregulate the conductivity thereof can include halogen salts, sodiumsalts, potassium salts, or a combination thereof. The one or more saltsadded to the water to regulate the conductivity thereof can includesodium chloride.

The galvanic cell can generate a current when immersed in the water. Theamount of current generated by the electrical cell can be any suitableamount of current, such as about 0.001 mA/cm² to about 10 mA/cm², 0.01mA/cm² to about 0.5 mA mA/cm², or less than, equal to, or greater thanabout 0.001 mA/cm², 0.005, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04,0.045, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35,0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 2, 2.5, 3, 4, 5, 6, 7,8, 9, or about 10 mA/cm² or more.

The immersing of the galvanic cell in the water can be sufficient tooxidize the phosphorus in the water. The method can be free of treatingthe water with an oxidizer or an oxidative treatment other than anyoxidation that occurs due to immersion of the galvanic cell in thewater. In some embodiments, the method includes oxidizing phosphorus inthe water prior to the immersion of the galvanic cell in the water,during the immersion of the galvanic cell in the water, or a combinationthereof. The method can include oxidizing phosphorus in the water priorto the immersion of the galvanic cell in the water. Oxidizing thephosphorus in the water can include contacting an oxidizer and the waterto oxidize the phosphorus (e.g., to oxidize phosphorus in organic matteror solid matter that contains phosphorus). An aqueous solution of theoxidizer can be added to the water. The aqueous solution of the oxidizerhas a concentration of the oxidizer of about 0.001 ppm to about 999,999ppm, about 50,000 ppm to about 140,000 ppm, or less than, equal to, orgreater than about 0.001 ppm, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 5,10, 15, 20, 50, 100, 150, 200, 500, 1,000, 1,100, 1,200, 1,500, 2,000,2,500, 5,000, 10,000, 15,000, 20,000, 50,000, 100,000, 150,000, 200,000,500,000, 750,000, or about 999,999 ppm or more. The oxidizer can be anysuitable oxidizer that oxidizes the phosphorus. The oxidizer can includeferrate, ozone, ferric chloride (FeCl₃), potassium permanganate,potassium dichromate, potassium chlorate, potassium persulfate, sodiumpersulfate, perchloric acid, peracetic acid, potassium monopersulfate,hydrogen peroxide, sodium hypochlorite, potassium hypochlorite,hydroxide, sulfite, a free radical via decomposition thereof, or acombination thereof. Sufficient oxidizer can be added, and sufficienttreatment conditions used, such that the oxidizer converts substantiallyall dissolved phosphorus in the water into oxidized forms of phosphorus.

Byproducts of an oxidation process can include negatively charged ioniccompounds that readily accept electrons and as a result arepreferentially reduced at the surface of copper in the galvanic cell.Many of these compounds have very low regulatory limits, and thegalvanic process can be used to remove or reduce the concentration ofone or more of these highly regulated compounds prior to the dischargeor reuse of the treated water. Examples of the most common compoundsthat can be reduced or removed are chloramines, chlorates, perchlorates,bromates, hypochlorous acid, bleach, and the like, organic compounds,and combinations thereof. Further, the galvanic phosphorus removal stagecan reduce the oxygen levels in the water to values below 1 ppm, thuscreating attractive condition for subsequent anoxic or anaerobicprocesses.

The method can be free of performing any steps to adjust pH of thetreated water. In some embodiments, the method can include adjusting thepH of the treated water to be about 6 to 8, or about 7, or less than,equal to, or greater than about 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7,6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, or about 8 ormore.

The method can include immersing one or more of the galvanic cells in anenclosure including the water. The method can include filtering the saltincluding the phosphorus from the treated water via one of more filtersthat are at least partially submerged in the water that immerses thegalvanic cells. The filter can include a glass frit, a fabric filter, apaper filter, a disk filter, a rotary filter, a drum filter, a screen, asieve, particulate filtration media, a filter aid, or a combinationthereof. The filter can be a rotating disk filter. The filtering caninclude forming a filter cake on the filter, the filter cake includingthe salt including the phosphorus. The filtering can include backwashingthe filter to remove the filter cake from the filter and to form abackwash liquor that includes the removed filter cake. Any suitablewater can be used to backwash the filter, such as a portion of the waterincluding the precipitate is used to backwash the filter.

The one or more galvanic cells can be positioned in the water at sideportions of the enclosure, wherein the filter is positionedapproximately in a central portion of the enclosure in the water suchthat the filter is in-between the plurality of galvanic cells. Themethod can include using a plurality of filters. The plurality offilters can include a plurality of rotating disk filters.

The galvanic cell can include an anode including Mg, Al, Fe, Zn, or acombination thereof. The galvanic cell can include a cathode includingCu, Ni, Fe, or a combination thereof. The galvanic cell can also includea conductive connector that electrically connects the anode and thecathode, the conductive connector including Cu, Zn, Fe, Cd, Ni, Sn,

Pb, or a combination thereof. In some embodiments, the anode and thecathode directly contact one another and the galvanic cell is free ofthe conductive connector, such that the electrodes are in an“electroless” configuration. In an electroless configuration, thesacrificial anode material can be galvanically plated or deposited onthe non-sacrificial cathode material, eliminating a need for conductiveconnectors to electrically connect the anode and the cathode. Oneadvantage of various embodiments of the electroless configuration isthat less metallic copper can be used and the electric drop between theelectrodes can decrease compared to the configuration includingconductive connectors.

The galvanic cell can include one cathode, or a plurality of cathodes.The galvanic cell can include one anode, or a plurality of anodes. Thegalvanic cell can include no conductive connector, one conductiveconnector, or a plurality of conductive connectors. The galvanic cellcan include a plurality of conductive connectors, wherein eachconductive connector independently electrically connects the anode andcathode (e.g., in a parallel, rather than a series configuration). Theplurality of conductive connectors can be approximately evenlydistributed around a perimeter of the galvanic cell. The conductiveconnector can include a connector or fastener, such as a screw, a bolt,a nut, a washer, or a combination thereof.

The galvanic cell can be of any suitable size or configuration such thatthe surface area of the galvanic cell(s) per unit volume of watercontaining phosphorus to be removed is sufficient to effect removal ofthe phosphorus during the residence time of the water in the container.The galvanic cell can have any suitable total surface area per galvaniccell, or total anode surface area exposed to water per cell, such asabout 1 cm² to about 1,000,000 cm², about 5 cm² to about 200,000 cm²,about 10 cm² to about 50,000 cm², about 20 cm² to about 40,000 cm², orabout 1 cm² or less, or less than, equal to, or greater than 2 cm², 4,6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 75, 100, 150, 200, 250, 500,750, 1,000, 1,500, 2,000, 2,500, 5,000, 7,500, 10,000, 15,000, 20,000,25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 75,000, 100,000,150,000, 200,000, 500,000, 750,000, or about 1,000,000 cm² or more. Thegalvanic cell can have any suitable ratio of anode surface area tocathode surface area, such as a ratio of anode surface area exposed towater to cathode surface area exposed to water, such as about 0.1 toabout 10, 0.5 to 2, or less than, equal to, or greater than about 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5,1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.8, 3, 3.5, 4,4.5, 5, 5.5, 6, 7, 8, 9, or about 10 more. In some embodiments, theanode, the cathode, or a combination thereof, includes a roughened oretched surface for enhanced surface area. For the methods describedherein, any suitable number of galvanic cells can be used, such as 1, 1to 1,000,000, 1 to 1,000, 1 to 20, or less than, equal to, or greaterthan 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45,50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 300, 400, 500,750, 1,000, 1,250, 1,500, 1,750, 2,000, 2,500, 3,000, 4,000, 5,000,10,000, 20,000, 50,000, 100,000, 250,000, 500,000, or about 1,000,000 ormore. The cells can be used in series or parallel electricalarrangement.

The galvanic cell can include a spacing between a surface of the anodeand a surface of the cathode (e.g., between the cathode and at leastabout 50% to 100% of the surface area of the anode, or about 80% toabout 100%, or less than, equal to, or greater than about 50%, 55, 60,65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or about 99% or more) of about 1mm to about 110 mm, or about 2 mm to about 30 mm, or less than, equalto, or greater than about 1 mm, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32,34, 36, 38, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, orabout 110 mm or more.

The galvanic cell can be planar in form, having a thickness that is lessthan a height and width. The galvanic cell can include a planar frame ofthe galvanic cell and a cathode material included within a perimeter ofthe frame, wherein the cathode material is electrically connected to theframe (e.g., via direct contact thereto). The frame can be a structuralcomponent of the galvanic cell. The frame can be structurally sufficientto maintain its shape in the absence of any of or all of the anodes. Theplanar frame and the cathode material included within the perimeter ofthe frame can both be the cathode.

The planar frame can be a nonporous solid material. The planar frame canbe one or more strips of cathode material assembled to form the frame.The planar frame can have a polygonal perimeter, such as a square orrectangle. The cathode material included within the perimeter of theplanar frame can include a porous cathode material, such as includingwire, mesh, screen, a sheet including one or more through-holes, or acombination thereof. The porous cathode material can include a wire meshor a wire screen including the porous cathode material. The porouscathode material included within the perimeter of the planar frame canhave edges that are sandwiched between two of the planar frames, the twoplanar frames held together to secure the porous cathode materialtherebetween with one or more of the conductive connectors, such as viacompression, via conductive connectors passing through one or morethrough-holes of the porous cathode material, or a combination thereof.

The galvanic cell can include a plurality of pairs of the planar frames(e.g., 2 pairs to 20 pairs, or 2 pairs to 10 pairs, or less than, equalto, or greater than 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, or 20 or more pairs), with each pair held together to securethe porous cathode material therebetween with one or more of theconductive connectors, and each pair separated by one or more of theanodes spanning across the porous cathode material included within theperimeter of the planar frame. The one or more anodes that separate eachpair of planar frames from one another can directly contact a face ofeach pair of planar frames separated therewith. The one or more anodesthat separate each pair of planar frames from one another can directlycontact a face of one of each pair of planar frames separated therewithand can be free of direct contact with a face of the other of each pairof planar frames separated therewith.

The anode can be a strip fastened to the planar frame at two edges ofthe planar frame, wherein the anode is fastened to the planar frame withat least one of the conductive connectors at each of the two edges ofthe planar frame, such that the anode spans across the cathode materialincluded within the perimeter of the planar frame forming a gap betweenthe cathode material included within the perimeter of the planar frameand the anode strip. The anode and the cathode can directly contact oneanother at each of the edges of the planar frame where the anode isfastened to the planar frame via the at least one conductive connector.

The galvanic cell can include a plurality of the anodes, wherein eachanode is a strip fastened to the planar frame at two edges of the planarframe on a face of the frame, wherein each of the anodes is fastened tothe planar frame with at least one of the conductive connectors at eachof the two edges of the planar frame, such that each of the anodes spansacross the cathode material included within the perimeter of the planarframe forming a gap between the cathode material included within theperimeter of the planar frame and the anode strip, wherein the pluralityof the anodes are spaced-apart across the face of the such that they donot physically contact one another. Each of the anodes can span acrossthe cathode material included within the perimeter of the planar frameapproximately parallel to one another on the face; anodes on anotherface of the planar frame can be parallel or perpendicular to the anodeson the first face. The two edges of the planar frame to which arefastened each anode can be opposite edges of the planar frame. Thegalvanic cell can have all of its anodes on a single major face of theplanar frame, or some of the anodes can be on one major face of theplanar frame and the other anodes are on another major face of theframe.

FIG. 1A illustrates a galvanic cell 110 viewed from a major face,according to various embodiments. The galvanic cell 110 includes thecathode, wherein the cathode includes a planar frame 120 of the galvaniccell having a polygonal perimeter and a porous material 130 includedwithin the perimeter of the frame that is a wire mesh or a wire screenthat is in direct contact with the frame. The galvanic cell 110 includesa plurality of the anodes 140, wherein each anode is a strip fastened tothe planar frame at two opposite edges of the planar frame on a face ofthe planar frame. Each of the anodes is fastened to the planar framewith at least one of the conductive connectors 150 at each of the twoedges of the planar frame, such that each of the anodes areapproximately parallel to one another and span across the porousmaterial included within the perimeter of the planar frame forming a gap(not shown) between the porous material included within the perimeter ofthe planar frame and the anode strip. Each anode directly contacts thecathode frame at each of the edges of the planar frame where the anodeis fastened to the planar frame via the at least one conductiveconnector. Conductive connectors (not shown) can also be used that onlypass through the planar frame 120 to secure the porous material 130therebetween. The plurality of the anodes are spaced-apart across theface of the such that they do not physically contact one another, andwherein the gap (not shown) is about 1 mm to about 110 mm.

FIG. 1B illustrates a zoomed-in cutaway edge-view of galvanic cell 110,viewed along the perspective shown to the right of FIG. 1A. The galvaniccell can include a plurality of pairs of the planar frames 120, witheach pair held together to secure the porous cathode material 130therebetween with one or more of the conductive connectors (not shown).Anodes 140 spanning across the porous cathode material 130 includedwithin the perimeter of the planar frame 120. Each pair of planar frames120 is separated by anodes 140 (only one such anode is shown in FIG.1B). The one or more anodes 140 that separate each pair of planar framesfrom one another directly contact a face of each pair of planar frames120 separated therewith.

In various embodiments, the galvanic phosphorus removal stage can alsoreduce the concentration of or remove other toxic or regulatedmaterials, such as materials formed during the electrolytic removal ofnitrogen stage, such as oxidizing materials (e.g., chlorate, chlorite,bromate, and the like). Such oxidizing species can polarize the galvaniccell, which can favor the oxidation kinetics of metallic aluminum.

In embodiments of the galvanic cell including aluminum in the anode, thedissolution of the aluminum anode during the operation of the galvaniccell can generate high localized concentrations of aluminum ions on orvery near the surface of the electrode which can favor thesupersaturation and thermodynamic conditions for the precipitation ofaluminum phosphate compounds. This surface condition can create a lowmetal-to-phosphorus molar ratio, even when phosphorus levels in waterare below 0.1 ppm. The resulting equilibrium concentration of phosphateremaining in solution can be much lower than those obtained by simplyadding aluminum salts to the water. When adding aluminum salts tophosphate-containing waters with the intent to obtain phosphorousconcentrations below about 0.1 ppm, the metal-to-phosphorus molar ratiosmust be close to 8. In contrast, in the galvanic process describedherein, the molar ratio of metal to phosphorus can be less than 8, suchas approximately 1.

Optional Further Removal of Nitrogen Stage.

The method of removing phosphorus and nitrogen optionally includes(e.g., either includes, or is free of) one or more additional stages forremoving nitrogen from the water after the water has passed through thegalvanic phosphorus removal stage. The one or more additional stages caninclude any suitable method of removing additional nitrogen from thewater.

In some embodiments, the optional further removal of nitrogen stageincludes removal of nitrate. The optional further removal of nitrogencan include exposing the water to denitrifying bacteria to convertwater-soluble nitrogen therein to nitrogen gas that is removed, such asdescribed in WO 2020/046679 which is hereby incorporated by reference inits entirety. The method can include deoxygenating the water prior tothe further removing of nitrogen therefrom. The method can includeoxidizing or hydrolyzing at least some nitrogen in the water to formnitrate prior to the further removing of nitrogen therefrom. The methodcan include reoxygenating the water after the further removing ofnitrogen therefrom.

In some embodiments, the optional further removal of nitrogen stageincludes optionally oxidizing or hydrolyzing at least some nitrogen inthe water to form nitrate; optionally deoxygenating the water to anoxygen concentration of about 0 ppm to about 0.3 ppm; exposing the waterto denitrifying bacteria immobilized on a porous substrate, to convertnitrate in the water to nitrogen gas that is removed and to form adenitrified water; and optionally reoxygenating the denitrified water toan oxygen concentration of about 1 ppm to about 20 ppm.

The denitrified water can have a total nitrogen concentration that isabout 0.0 ppm to about 2 ppm total nitrogen.

Method of Removing Nitrogen from Water.

Various embodiments of the present invention provide a method ofremoving nitrogen from water. The method can include passing the waterthrough an electrolytic cell to remove nitrogen from the water asnitrogen gas. The method can include any feature described herein forthe electrolytic nitrogen removal stage.

Prior to passing through the electrolytic cell, the water can have anysuitable chloride concentration, such as 50 ppm to 40,000 ppm, 200 ppmto 10,000 ppm, or 50 ppm or more, or less than, equal to, or greaterthan 100 ppm, 200, 500, 1,000, 2,000, 4,000, 6,000, 8,000, 10,000,15,000, 20,000, 30,000, or 40,000 ppm or less.

The water can be passed through a single electrolytic cell, or aplurality of electrolytic cells. The water passed through theelectrolytic cell is allowed to contact the anode and cathode and can beallowed to flow between the anode and cathode. Water passing through theelectrolytic cell can partially or fully submerge/immerse theelectrolytic cell. Shear can be applied to the water as it is passedthrough the electrolytic cell, to increase exposure of the water to thecathode and anode surfaces.

The water immersing the electrolytic cell can have any suitable pH, suchas a pH of 6 to 12, 6 to 7, or 6 or more, or less than, equal to, orgreater than 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12 orless. The method can include adding one or more bases to the water toregulate or maintain the pH of the water, such as sodium hydroxide; inother embodiments, the method is free of adding acids or bases to thewater to maintain or regulate the pH thereof.

The electrolytic cell can be operated in any suitable way to removenitrogen as nitrogen gas from the water. The cell can be operated withDC current or AC current. The electrolytic cell can be operated with anysuitable current density, such as 0.001-0.1 A/cm², 0.02-0.04 A/cm², or0.001 A/cm² or more, or less than, equal to, or greater than 0.005,0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06, 0.07,0.08, 0.09, or 0.1 A/cm² or less.

The electrolytic cell includes an anode. The anode can include titaniumoxide, ruthenium oxide, and iridium oxide supported on titanium(TiO₂—RuO₂—IrO₂/Ti); or titanium oxide and ruthenium oxide supported ontitanium (TiO₂—RuO₂/Ti); or titanium and platinum (Ti—Pt); or acombination thereof. The anode and cathode materials can be selectedsuch that the electrodes favor the formation of chlorine gas to formhypochlorite during operation of the electrolytic cell.

The electrolytic cell includes a cathode. The cathode can includetitanium, stainless steel, or a combination thereof. The cathode caninclude stainless steel.

The electrolytic cell can include a spacing between the anode andcathode, such as a spacing of 0.5-8 mm, 2-4 mm, or 0.5 mm or more, orless than, equal to, or greater than 1 mm, 1.5, 2, 2.5, 3, 3.5, 4, 4.5,5, 6, 7, or 8mm or less.

The method is not limited to any particular mechanism of removingnitrogen from the water as ammonia using the electrolytic cell. Theremoving of nitrogen as nitrogen gas can include converting ammonia inthe water to nitrogen gas using the electrolytic cell. Passing the waterthrough the electrolytic nitrogen removal stage can produce hypochloritein the water which can react with ammonia in the water to form thenitrogen gas, which can be released to the environment. The electrolyticcell can produce any suitable hypochlorite concentration in the waterbeing passed therethrough, such as 100-20,000 ppm hypochlorite,2000-2500 ppm, or 100 ppm or more, or less than, equal to, or greaterthan 200 ppm, 400, 600, 800, 1,000, 1,200, 1,400, 1,600, 1,800, 2,000,2,100, 2,200, 2,300, 2,400, 2,500, 2,600, 2,800, 3,000, 4,000, 6,000,8,000, 10,000, 15,000, or 20,000 ppm or less.

The method can remove any suitable amount of nitrogen from the water.For example, passing the water through the electrolytic nitrogen removalstage can remove 80% to 100% of ammonia from the water, 99-100%, or 80%or more, or less than, equal to, or greater than 81%, 82, 83, 84, 85,86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or99.999% or less.

In various embodiments, the method of removing nitrogen from the wateras nitrogen gas can also include removing phosphorus from the water,such as any suitable amount of phosphorus. For example, passing thewater through the electrolytic nitrogen removal stage can remove 0.1 to90% of reactive phosphorus from the water, or 1-30%, or 0.1% or more, orless than, equal to, or greater than 2%, 4, 6, 8, 10, 12, 14, 16, 18,20, 22, 24, 26, 28, 30, 40, 50, 60, 70, 80, or 90% or less.

System for Removal of Nitrogen and Phosphorus from Water.

Various embodiments of the present invention provide a system forremoval of nitrogen and phosphorus from water. The system can be anysuitable system that can perform the method for removing nitrogen andphosphorus from water described herein. The system can include anelevated pH phosphorus removal stage configured to raise pH of startingmaterial water to greater than or equal to 7.5 to precipitate aphosphorus salt from the water and configured to remove the precipitatedphosphorus salt from the water. The system can include an electrolyticnitrogen removal stage including an electrolytic cell configured toremove nitrogen from the water as nitrogen gas. The system can include agalvanic phosphorus removal stage including a galvanic cell including ananode including Mg, Al, Fe, Zn, or a combination thereof, and a cathodehaving a different composition than the anode, the cathode including Cu,Ni, Fe, or a combination thereof. The galvanic cell can be configured toform a treated water including a salt that includes phosphorus from thewater. The galvanic phosphorus removal stage can be configured toseparate the salt including the phosphorus from the treated water. Thewater produced by the system has a lower phosphorus concentration and alower nitrogen concentration than the starting material water.

Apparatus for Removal of Nitrogen from Water.

Various embodiments of the present invention provide an apparatus forremoval of nitrogen from water. The apparatus can be any suitableapparatus that can perform the method for removing nitrogen from waterdescribed herein. The apparatus can include an electrolytic cell throughwhich water is configured to be flowed to remove nitrogen from the wateras nitrogen gas. The electrolytic cell includes a cathode that caninclude stainless steel and/or titanium. The electrolytic cell includesan anode that can include titanium oxide, ruthenium oxide, and iridiumoxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti); or titanium oxide andruthenium oxide supported on titanium (TiO₂—RuO₂/Ti); or titanium andplatinum (Ti—Pt); or a combination thereof. The anode and cathodematerials can be selected such that the electrodes favor the formationof chlorine gas to form hypochlorite during operation of theelectrolytic cell. Using the apparatus to remove nitrogen as nitrogengas can remove 80-100% of ammonia from the water.

EXAMPLES

Various embodiments of the present invention can be better understood byreference to the following Examples which are offered by way ofillustration. The present invention is not limited to the Examples givenherein.

Galvanic cells of several sizes were utilized to evaluate aspects of theprocess as outlined in the Examples. The galvanic cells are referencedas “small”, “medium”, and “large”, as defined below. Magnesium anodeswere AZ91, with 90 wt % Mg, 9 wt % Al, and 1 wt % Zn, and were 99.9 wt %pure. Aluminum anodes were 99.9 wt % pure aluminum. The copper used incopper frames and copper mesh was 99.9 wt % pure copper.

For a small-sized cell, having copper cathodes and either an aluminum ormagnesium anode, the finished size was 5 cm×20 cm with a thickness ofabout 4 mm and utilized copper meshes and an anode having a thickness ofabout 1 mm each. The small-sized cell included a single pair of coppermeshes with an anode sandwiched therebetween, with the copper meshes andthe anode separated from the copper meshes by 0.5 cm using electricallyinsulating plastic screws. The copper meshes were electrically connectedto one another via a copper wire. The anode and the cathode were notelectrically connected to one another (other than via multimeter and thesurrounding water). The resulting surface area of sacrificial anodeexposed to the water was about 400 mm² per cell. FIG. 2A illustrates aphotograph along the edge of an Al—Cu electrochemical cell

For a medium-sized cell, having a copper cathode and either aluminum ormagnesium anodes, the finished size was about 300 mm×45 mm with athickness of about 10 mm and utilized a single pair of copper mesheswith an anode sandwiched therebetween. The copper mesh directlycontacted the anode, and was connected thereto via brass bolts (commonbrass, 67 wt % copper and 33 wt % Zn). The resulting surface area ofsacrificial anode exposed to the water was about 31,400 mm² per cell.FIG. 2B illustrates a photograph along an edge of a plurality ofmedium-sized Al—Cu electrochemical cells.

The large-sized electrochemical cells used in the Examples includedcathodes that are pairs of planar solid copper frames that sandwich acopper mesh, with brass connectors securing the copper frames togetherto secure the copper mesh between the frames. The solid copper framesformed a rigid structural perimeter of the cell, with the copper meshfilling the entire area within the perimeter of each pair of copperframes. A plurality of anode strips, which were magnesium alloy oraluminum, were fastened to the perimeter of the frame with brassfasteners such that they spanned from one edge of the frame to the otherframe, directly contacting the frame and forming a gap between theanodes and the copper mesh. Each electrochemical cell included two pairsof the copper frames having the copper mesh therebetween (i.e., fourcopper frames total, with two copper meshes). A first pair of copperframes had anodes affixed to a single major face thereof, the secondpair of copper frames had anodes affixed to both major faces thereof,with the two pairs of copper frames affixed to one another with brassfasteners such that they do not directly contact one another and suchthat they sandwich the anodes affixed to one major face of the secondpair of copper frames. The brass fasteners were common brass and were 67wt % copper and 33 wt % Zn. The anodes ran horizontally across eachmajor face of the copper frames and parallel to one another, with 6anodes affixed to each face. From one major face of the electrochemicalcell to the other, the order of components is 1) the anodes affixed to amajor face of the first pair of copper frames, 2) the first pair ofcopper frames having copper mesh therebetween, 3) the anodes affixed toa major face of the second pair of copper frames, 4) the second pair ofcopper frames having copper mesh therebetween, and 5) the anodes affixedto the other major face of the second pair of copper frames. The ratioof anode surface area to cathode surface area for the electrochemicalcell was about 1:1.

For a large-sized cell, each copper frame had a thickness of 3.175 mm (⅛inch). The height of the copper frame was 400 mm and the length of thecopper frame was 400 mm. The copper mesh had a thickness of 1.5875 mm,such that each pair of copper frames sandwiching the copper mesh had athickness of about 8 mm. The anode strips had a length of 400 mm, awidth of 45 mm, and a thickness of 6 mm. The thickness of the entireelectrochemical cell was about 30 mm. The gap between the anodes on eachface of the copper frames was 12-18 mm. The gap between the anodesaffixed to each pair of copper frames and the copper mesh sandwichedtherebetween was 12-18 mm. The large-sized cell using aluminum anodesincluded an anode surface area exposed to the water of about 290,000mm², and the large-sized cell using magnesium included an anode surfacearea exposed to the water of about 868,000 mm².

FIG. 2C illustrates a photograph of a major face of the large-sizedMg—Cu electrochemical cell used in the Examples. FIGS. 2D and 2Eillustrate close-up photographs of an edge of the large-sized Mg—Cuelectrochemical cell used in the Examples.

In the Examples herein, the Al—Cu or Mg—Cu electrochemical cell wascompletely immersed in water in a container, such that electrochemicalcell was vertically oriented with the anodes running vertically. Whenmultiple electrochemical cells were used, they were separated by about25 mm using a wooden frame. In the middle of the container a mechanicalstirrer was used to agitate the water therein. Water was filtered andfed into the container using a pump.

Another pump was used to circulate water and filter water within thecontainer (e.g., to remove precipitate therefrom), with water pumpedfrom one side of the container and recirculated to the other side. Apump connected to a reservoir of 10% HCl was used to add HCl to thecontainer to adjust the pH of the water therein. The water in thecontainer was measured to determine the pH thereof, which was used todetermine the amount of acid that needed to be added from the reservoirto maintain a specific pH. The water fed into the container was analyzedto determine initial pH, initial conductivity, and initial reactivephosphorus content. For the Mg—Cu cell, the water fed into the containerwas also analyzed to determine the initial dissolved magnesium content.The pH and conductivity of water in the container was measured. Thecontainer included a drain at the water level of the container to allowwater to exit the system. The water that exited the system was analyzedto determine the final pH, final conductivity, and final reactivephosphorus content. For the Al—Cu cell, the water exiting the containingwas analyzed to determine the total Al and dissolved Al. For the Mg—Cucell, the water exiting the container was analyzed to determine thedissolved magnesium content. FIG. 2F illustrates a photograph showing atop-view of the system used in the Examples, with the specificembodiment shown in the photograph having 12 electrochemical cells (6 infront, and 6 in back arranged edge-to-edge with the 6 in front). FIG. 2Gillustrates a photograph showing a side-view of the system used in theExamples, with the specific embodiment having 12 electrochemical cellstherein.

The “reactive phosphorus concentration” refers to the soluble reactivephosphorus in solution (e.g., orthophosphate) and was measured by US-EPA365.1: Determination of Phosphorus by Semi-Automated Colorimetry. The pHwas measured using an Oakton® pH 700 meter. The conductivity wasmeasured using an Oakton® CON 150 meter. The dissolved magnesium contentwas measured using a Thermo Scientific™ Dionex™ Aquion™ ionchromatography system. The total aluminum content and dissolved aluminumcontent were measured using a Hach Aluminum TNT plus™ vial test.Dissolved Al was determined at the pH of the water exiting thecontainer. Total Al was determined by adjusting the pH to 2.

Part I. Galvanic Cell. Example 1 Removal of Phosphorus with Al—Cu Cell,Initial P Concentration 0.033 ppm

Water was taken from one of the channels of a local lake and theresidence time in the galvanic process was modified by adjusting thewater flow to provide specific residence times while keeping the othervariables of the system constant (pH, conductivity, and concentration ofphosphorus). Residence time (i.e., volume of the container divided bythe flow rate) was gradually decreased until removal performance wasreduced and then held constant for this Example. For a low initialconcentration of phosphorus (0.033 ppm) residence time was reduced toapproximately 15 min while maintaining an average of about 90% removalof phosphorus. The Al—Cu cell was medium-sized. The results are shown inTable 1.

TABLE 1 Removal of phosphorus with Al—Cu cell, initial P concentration0.033 Water Source Local Lake (C44) Flow Rate (mL/min) 650 950 1261Residence Time (mins) 30 20 15 Electrochemical cells 8 8 8 Initial pH8.43 8.43 8.43 Final pH 7.05 7.03 7.02 Initial Conductivity (μS) 776 776776 Final Conductivity (μS) 778 778 778 Initial reactive-P (ppm) 0.0330.033 0.033 Final reactive-P (ppm) 0.0028 0.0028 0.0027 % P removal 91.591.5 91.5 Final total Al (ppm) 1.18 1.00 1.00 Final dissolved Al (ppm)0.134 0.115 0.110ppm.

Example 2 Removal of Phosphorus with Al—Cu Cell, Initial P Concentration0.451 ppm

Water from a local inland wastewater treatment facility was processed toevaluate the effect of increasing solution conductivity. Residence timewas held constant during this Example at 21 min. Conductivity wasmodified by adding NaCl. This Example demonstrates the beneficial effectof increased conductivity on the effectiveness of phosphorus removal.The Al—Cu cell was medium-sized. The results are shown in Table 2.

TABLE 2 Removal of phosphorus with Al—Cu cell, initial P concentration0.451 ppm. Cell size = medium. Water Source Inland Wastewater Plant FlowRate (mL/min) 920 920 Residence Time (mins) 21 21 Electrochemical cells8 8 Initial pH 7.69 7.69 Final pH 7.02 6.93 Initial Conductivity (μS)673 960 Final Conductivity (μS) 672 962 Initial reactive-P (ppm) 0.4510.451 Final reactive-P (ppm) 0.062 0.027 % P removal 86.3 94.0 Finaltotal Al (ppm) 1.15 1.81 Final dissolved Al (ppm) 0.037 0.056

Example 3 Removal of Phosphorus with Al—Cu Cell, Initial P Concentration0.392 ppm

A coastal wastewater treatment plant effluent with high electricalconductivity was treated using the medium Al—Cu cell. As noted inExample 2 above, increased conductivity is beneficial. The water treatedin this Example was from a coastal location where the salt (NaCl)concentration results in elevated conductivity. The purpose of thisExample is to evaluate the loss of sacrificial electrode material to thetreated water solution and to evaluate this relationship as a functionof pH. The final phosphorus removal efficiency remained constant;

however, the concentration of total aluminum (dissolved and solid)decreases when modifying the pH from pH 7 to pH 6.5. This Exampledemonstrates the ability to control the loss of material from thesacrificial electrode by adjusting the pH. The results are shown inTable 3.

TABLE 3 Removal of phosphorus with Al—Cu cell, initial P concentration0.392 ppm. Cell size = medium. Water Source Coastal Wastewater FacilityFlow Rate (mL/min) 920 920 Residence Time (mins) 21 21 Electrochemicalcells 8 8 Initial pH 9.06 9.06 Final pH 7.00 6.47 Initial Conductivity(μS) 3100 3100 Final Conductivity (μS) 3141 3110 Initial reactive-P(ppm) 0.392 0.392 Final reactive-P (ppm) 0.042 0.032 % P removal 89.391.8 Final total Al (ppm) 2.24 1.90 Final dissolved Al (ppm) 0.055 0.059

Example 4 Removal of Phosphorus with Al—Cu Cell, Initial P Concentration0.648-0.762 ppm

Water from a local fresh water retention pond was spiked with phosphoricacid to obtain a concentration of 0.75 ppm of phosphorus and was treatedutilizing multiple galvanic cells in a continuous flow apparatus with aflow of about 2 gallons per minute (GPM) (large cell). The pH of thewater was adjusted incrementally downward to values between 7 and 6. Anincrease the percentage of removal from 82% at pH=7 to 97% at pH=6 wasobserved, while reducing the soluble aluminum remaining in the treatedwater. The results are shown in Table 4.

TABLE 4 Removal of phosphorus with Al—Cu cell, initial P concentration0.648-0.762 ppm. Cell size = large. Water Source Retention Pond FlowRate (mL/min) 7797.1 7797.1 7797.1 Residence Time (mins) 20-25 20-2520-25 Electrochemical cells 12 12 12 Initial pH 7.03 7.06 7.03 Final pH6.96 6.5 5.95 Initial Conductivity (μS) 680.9 689 680.9 FinalConductivity (μS) 671.7 676.3 695.4 Initial reactive-P (ppm) 0.742 0.6480.762 Final reactive-P (ppm) 0.135 0.047 0.024 % P removal 81.8 92.796.9 Final total Al (ppm) 3.17 2.78 4.38 Final dissolved Al (ppm) 0.0350.029 0.028

Example 5 Conductivity Effects on Electrical Current Generated by Al—CuCell Versus Time

Using a small-sized cell, Al-foil and Cu screens having a size of 5 cm×2cm were separated by 0.5 cm using plastic screws. The Al-foil/Cu wasplaced in a simple compartment with magnetic stirring that was filledwith 30 mL water from a local freshwater retention pond. The currentswere measured with a Keithley 175 multimeter connected in series. Theinitial conductivity was adjusted with NaCl. The electrical currentgenerated by the Al—Cu galvanic pair in the Al—Cu cell was measured.This electric current is a measure of the amount of the anode materialthat was transformed in the electrodes as a function of time, e.g., theoxidation reaction of aluminum to generate aluminum ions and thedecomposition of water on the copper electrode to generate hydrogen andhydroxyl ions.

FIG. 3 shows the variation of the electric current that was generated bythe Al—Cu galvanic pair as a function of the conductivity of thesolution. The initial pH of the water was not modified and was about 7.An increase of the initial conductivity of the solution up to a value of1000 μS increases the electric current due to a decrease in theresistance between the electrodes thereby increasing the rate of thechemical reactions at the electrode surface. A similar result wasobtained in Example 2. Increasing the conductivity to values higher than1000 μS resulted in little change in the electrical current because athigher conductivity values the rate limiting step of the reaction is thekinetics of the chemical processes at the surface of the electrodes.

Example 6 pH Effects on Electrical Current Generated by Al—Cu CellVersus Time

The same experimental conditions as Example 5 were used, but adjustingthe initial pH with NaOH, with the initial conductivity of the wateradjusted with NaCl to about 1000 μS. FIG. 4 shows the variation of theelectric current generated by the Al—Cu galvanic pair as a function ofthe pH of the solution. Decreasing the pH of the solution favors thekinetics of the decomposition of water on the copper electrode, whichtranslates into an increase in electrical current by the Al—Cu galvanicpair.

Example 7 Conductivity Effects on Electrical Current Generated by Mg—CuCell Versus Time

The same experimental conditions as Example 5 were used, withoutmodification of pH, and with modification of conductivity using NaCl.FIG. 5A shows the variation of the electric current that circulates inthe Galvanic pair of Mg—Cu as a function of the water conductivity of alocal freshwater holding pond. The increase of the conductivity of thewater produces remarkable increases in the electric current of theelectrochemical cell. The effect of this increase in conductivity in thekinetics of chemical reactions is shown in FIG. 5B, where it improvesthe kinetics of the pH increase.

Example 8 Mg—Cu Cell, Initial P Concentration 0.392-0.451

Two bodies of water from treatment plants were compared; the watercollected from a coastal waste-water treatment plant (WWTP) has threetimes more conductivity than the water from an inland WWTP due to saltwater inclusion in the processing system. The higher conductivity favorsthe reaction kinetics and thus for the same residence time a greaterphosphorus removal occurs in the higher conductivity water whileconsuming the same amount of sacrificial anode (resulting in the sameamount of magnesium ions in solution) as with the lower conductivity.The Mg—Cu cell was medium-sized. The results are shown in Table 5.

TABLE 5 Mg—Cu cell, initial P concentration 0.392- 0.451. Cell size =medium. Inland WWTP Coastal WWTP Flow Rate (mL/min) 370 370 ResidenceTime (mins) 50 50 Electrodes 8 8 Initial pH 7.69 9.06 Final pH 10.9010.94 Initial Conductivity (uS) 960 3100 Final Conductivity (uS) 11243148 Initial reactive-P (ppm) 0.451 0.392 Final reactive-P (ppm) 0.1220.061 % P removal 72.9 84.4 Initial dissolved Magnesium (ppm) 17 56Final dissolved Magnesium (ppm) 44 95Part II. Galvanic Cell Used with Phosphorus Removal Stage andElectrolytic Nitrogen Removal Stage.

Example 9

Water obtained was remnant process water from a phosphate mine reservoirat around pH 4.3 and containing around 260 ppm NH₃, 120 ppm reactivephosphorus, 3600 ppm Na, 500 ppm Mg, 280 ppm Ca, and 5800 ppm chloride.The water was stored in 250-gallon totes to be used as influent water.

The influent water was pumped continuously from the tote at 100 mL/minby a Cole Parmer peristaltic pump and tubing into a 3-gallon tank calledthe mixing tank. Inside the mixing tank was a mixer to ensure goodmixing. Approximately 5% sodium hydroxide was dosed via a Cole Parmerpump and tubing at approximately 0.5 mL/min continuously to maintain amixing tank pH of 8.5. Anionic polymer flocculant dissolved in water(0.01%) was dosed in a similar manner to bring the mixing tankflocculant concentration to around 5 ppm. As the water entered themixing tank its pH would be brought up from 4.3 to 8.5 and calciumphosphate, struvite and other unknown precipitates formed. Total solidswere approximately 500 ppm. Solid concentration was determined byweighing the 5-micron filter bag after a set period and dividing bytotal flow over that time. The solids then contacted the flocculant,increasing particle size, and overflowed from the mixing tank into a5-micron bag filter. The solids were removed from the water, leavingbetween 4 and 8 ppm of reactive phosphorus and 180 to 200 ppm of NH₃—Nin the water. Reactive phosphorus, ammonia, and both free and totalchlorine was determined by HACH test kits and the appropriatecolorimetric method on the spectrophotometer.

After passing through the 5-micron bag filter, the flowed by gravityinto a 3-gallon settling tank to allow any remaining precipitates tosettle at the bottom of the tank. These solids were periodically cleanedout by passing the entire settling tank through the 5-micron filteragain as needed.

Water was then pumped from the top of the settling tank to theelectrolysis tank at 100 mL/min via a Cole Parmer peristaltic pump andtubing. This water is called post-settling tank water.

The electrolysis tank was a 1.5 L plastic vessel. Inside theelectrolysis tank was a mixer to ensure good mixing, and an electrode.The electrode was prepared using a 9″ by 2″ titanium oxide, rutheniumoxide, and iridium oxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti)screen as the anode, and a 9″ by 2″ 304 stainless steel screen as thecathode. Several plastic nuts and bolts were used to fix the anode andcathode approximately 2-4 mm apart from each other. One set of brassnuts and bolts were affixed separately through each the anode and thecathode screens to provide contact points for the DC power generator.The anode and cathode were connected to the DC power generator byalligator clips provided with the DC power generator. The DC powergenerator was set to provide power at 6.5 amps and around 4.2 V. Theelectrode produced between 2000 and 2500 ppm of bleach through oxidationof the chloride in solution.

Side reactions on the cathode would also cause precipitation of residualcalcium and phosphorus on the surface of the electrode, as well as adrop in pH. To maintain an appropriate pH of around 7, 2.5% sodiumhydroxide was dosed in a similar manner to the mixing tank. The bleachproduced reacts with the ammonia to produce nitrogen gas which isevolved to the atmosphere. The side reaction precipitates were cleanedoff the cathode manually as needed to remove them from the surface ofthe electrode. The entire electrolysis tank was dumped into the 5-micronfilter after the mixing tank to remove the solids from the water. Waterthen overflowed the electrolysis tank with between 0.1 and 2 ppmreactive phosphorus, 0 to 1 ppm NH₃, and 0 to 300 ppm residual free andtotal chlorine.

Water overflowed into the 1 L chlorine contact tank to allow theresidual chlorine to continue to react with any residual ammonia.Finally, water overflowed the chlorine contact tank with 0 to 300 ppmresidual free and total chlorine, 0 to 0.3 ppm NH3-N, and 0 to 2 ppmreactive phosphorus. Water from this point was recorded as effluentwater. A summary of the data is shown in Table 6. Water then flowed intothe galvanic system to have any residual phosphorus, bleach, andundesired oxidation byproducts removed.

TABLE 6 Example 9 data. Mixing tank pH = 8.5. All samples are averaged,and are given in ppm. HACH HACH HACH HACH Total Free Na K Mg Ca Cl NO₂Br SO₄ NO₃ reactive P NH₃ chlorine chlorine Influent 4023.81 258.89522.26 301.38 6263.96 0.00 19.56 3783.75 0.11 121.00 268.00 0.00 0 Post-4113.27 243.64 438.33 185.42 6287.68 0.00 18.89 3911.73 0.11 6.06 174.740.00 0 settling tank Effluent 4466.70 241.31 413.78 181.90 6130.76 0.0010.50 3841.10 8.16 1.01 1.28 5.15 4.9

Example 10 Evaluation of Increasing pH and the Resulting Phosphorus andAmmonia Removal

Example 10 was conducted in a similar way to Example 9 with the mainexception being that the mixing tank pH was adjusted to 9.3 and not 8.5.This change in pH resulted in around 4200 ppm of solids to precipitatein the mixing tank and combine with the flocculant to be filtered out.Water leaving the mixing tank had between 0 and 2 ppm reactivephosphorus and between 150 and 200 ppm NH₃—N after filtration throughthe 5-micron bag filter.

The water made its way to the electrolysis tank in a similar manner toExample 9. Once in the electrolysis cell, the electrolysis proceeded ina similar manner with the main exceptions being less solidsprecipitating on the stainless-steel cathode, less frequent cleaning ofthe cathode required, and less sodium hydroxide required to maintain theappropriate pH of 7. Water overflowed the electrolysis tank with 0 to0.5 ppm reactive phosphorus, 0 to 1 ppm NH₃—N, and 0 to 300 ppm residualfree and total chlorine.

Water overflowed into the 1 L chlorine contact tank to allow theresidual chlorine to continue to react with any residual ammonia.Finally, water overflowed the chlorine contact tank with 0 to 300 ppmresidual free and total chlorine, 0 to 0.3 ppm NH3-N, and 0 to 0.5 ppmreactive phosphorus. A summary of the data is shown in Table 7.

TABLE 7 Example 10 data. Mixing tank pH = 9.3. All samples are averaged,and are given in ppm. HACH HACH HACH HACH Total Free Na K Mg Ca Cl NO₂Br SO₄ NO₃ reactive P NH₃ chlorine chlorine Influent 3916.09 244.01517.33 282.73 7461.48 0.00 20.11 4368.30 3.06 144.40 260.00 0.00 0 Post-4268.89 248.96 435.97 126.82 5938.43 0.00 17.92 3531.69 0.00 1.19 179.000.00 0 settling tank Effluent 4415.53 240.53 391.67 126.77 5847.78 0.003.04 3557.15 9.28 0.22 0.33 24.50 18.5

Example 11 Evaluation of Current Density, the Resulting Production ofHypochlorite and Corresponding Reduction of Ammonia

Example 11 was performed in a similar manner to Example 10. In Example11, the effect of varying current densities on the production of bleachand the removal of ammonia was examined.

The water passed through the mixing tank, settling tank, electrolysistank, and contact tank in a similar manner as Example 10.

The current passed through the electrode was tested at 8 amps, 7.5 amps,7 amps, and 6.5 amps with other features remaining constant. Highercurrents produced more bleach than lower currents, as shown in Table 8,but all densities produced enough bleach to completely remove allammonia. 6.5 amps was found to be approximately optimal for theconcentration of ammonia in this Example.

TABLE 8 Example 11 data. Effect of current density on bleach production.All samples are averaged and are given in ppm unless otherwiseindicated. HACH HACH Current HACH HACH Total Free (amps) Na K Mg Ca ClNO₂ Br SO₄ NO₃ reactive P NH₃ chlorine chlorine Influent 3916.09 244.01517.33 282.73 7461.48 0.00 20.11 4368.30 3.06 144.40 260.00 0.00 0 Post-8.00 4174.58 260.06 427.65 114.75 6026.89 0.00 19.13 3533.59 0.29 1.36172.00 0.00 0 settling tank Effluent 8.00 4508.14 262.63 414.95 127.165943.88 0.00 5.80 3633.66 15.01 0.25 0.17 163.00 177 Post- 7.5 4229.63262.36 432.20 115.03 6065.58 0.00 19.49 3527.75 0.20 1.28 169.00 0.00 0settling tank Effluent 7.50 4443.67 255.31 388.65 113.20 5955.52 0.004.92 3604.57 12.84 0.15 0.13 158.00 142 Post- 7.00 4142.25 254.03 423.20119.52 6063.88 0.00 18.98 3593.83 0.26 1.26 173.00 0.00 0 settling tankEffluent 7.00 4354.75 246.74 379.66 109.21 5815.93 0.00 4.86 3468.0811.25 0.18 0.19 91.00 78 Post- 6.50 4147.71 256.42 426.90 124.55 5991.910.00 17.87 3539.38 0.00 1.23 174.00 0.00 0 settling tank Effluent 6.504302.04 248.59 392.33 109.00 5864.98 0.00 5.15 3522.07 9.40 0.33 0.2958.00 50

The terms and expressions that have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theembodiments of the present invention. Thus, it should be understood thatalthough the present invention has been specifically disclosed byspecific embodiments and optional features, modification and variationof the concepts herein disclosed may be resorted to by those of ordinaryskill in the art, and that such modifications and variations areconsidered to be within the scope of embodiments of the presentinvention.

Exemplary Embodiments

The following exemplary embodiments are provided, the numbering of whichis not to be construed as designating levels of importance:

Embodiment 1 provides a method of removing phosphorus and nitrogen fromwater, the method comprising:

-   -   passing starting material water comprising nitrogen and        phosphorus through an elevated pH phosphorus removal stage        comprising        -   raising pH of the water to greater than or equal to 7.5 to            precipitate a phosphorus salt from the water; and        -   removing the precipitated phosphorus salt from the water;    -   passing the water through an electrolytic nitrogen removal stage        comprising        -   passing the water through an electrolytic cell to remove            nitrogen from the water as nitrogen gas; and    -   passing the water through a galvanic phosphorus removal stage        comprising        -   immersing a galvanic cell in the water to form treated water            comprising a salt that comprises phosphorus from the water,            the galvanic cell comprising            -   an anode comprising Mg, Al, Fe, Zn, or a combination                thereof,            -   a cathode having a different composition than the anode,                the cathode comprising Cu, Ni, Fe, or a combination                thereof; and        -   separating the salt comprising the phosphorus from the            treated water;    -   wherein the water produced by the method has a lower phosphorus        concentration and a lower nitrogen concentration than the        starting material water.

Embodiment 2 provides the method of Embodiment 1, wherein the startingmaterial water is water from a phosphate mine reservoir.

Embodiment 3 provides the method of any one of Embodiments 1-2, whereinthe starting material water is water originated from a process ofdissolving phosphate-containing rock to produce phosphoric acid.

Embodiment 4 provides the method of any one of Embodiments 1-3, whereinthe starting material water has a pH of less than 7.5.

Embodiment 5 provides the method of any one of Embodiments 1-4, whereinthe starting material water has a pH of 4-5.

Embodiment 6 provides the method of any one of Embodiments 1-5, whereinthe phosphorus in the starting material water is in the form ofelemental phosphorus, inorganic phosphorus, organic phosphorus, adissolved form of phosphorus, a solid form of phosphorus, oxidizedphosphorus, or a combination thereof.

Embodiment 7 provides the method of any one of Embodiments 1-6, whereinthe starting material water has an ammonia concentration of 50 ppm to5,000 ppm.

Embodiment 8 provides the method of any one of Embodiments 1-7, whereinthe starting material water has an ammonia concentration of 150 ppm to400 ppm.

Embodiment 9 provides the method of any one of Embodiments 1-8, whereinthe starting material water has a reactive phosphorus concentration of10 ppm to 10,000 ppm.

Embodiment 10 provides the method of any one of Embodiments 1-9, whereinthe starting material water has a reactive phosphorus concentration of50 ppm to 400 ppm.

Embodiment 11 provides the method of any one of Embodiments 1-10,wherein the starting material water has a sodium concentration of 50 ppmto 20,000 ppm.

Embodiment 12 provides the method of any one of Embodiments 1-11,wherein the starting material water has a sodium concentration of 400ppm to 5,000 ppm.

Embodiment 13 provides the method of any one of Embodiments 1-12,wherein the starting material water has a magnesium concentration of 10ppm to 10,000 ppm.

Embodiment 14 provides the method of any one of Embodiments 1-13,wherein the starting material water has a magnesium concentration of 50ppm to 600 ppm.

Embodiment 15 provides the method of any one of Embodiments 1-14,wherein the starting material water has a chloride concentration of 50ppm to 40,000 ppm.

Embodiment 16 provides the method of any one of Embodiments 1-15,wherein the starting material water has a chloride concentration of 200ppm to 10,000 ppm.

Embodiment 17 provides the method of any one of Embodiments 1-16,wherein the water produced by the method has a total phosphorusconcentration of about 0 ppm to about 1 ppm.

Embodiment 18 provides the method of any one of Embodiments 1-17,wherein the water produced by the method has a total phosphorusconcentration of about 0.0001 ppm to 0.1 ppm.

Embodiment 19 provides the method of any one of Embodiments 1-18,wherein the water produced by the method has a total phosphorusconcentration of about 0.0001 ppm to 0.05 ppm.

Embodiment 20 provides the method of any one of Embodiments 1-19,wherein the water produced by the method has a dissolved phosphorusconcentration of about 0 ppm to about 1 ppm.

Embodiment 21 provides the method of any one of Embodiments 1-20,wherein the water produced by the method has a dissolved phosphorusconcentration of about 0.0001 ppm to 0.1 ppm.

Embodiment 22 provides the method of any one of Embodiments 1-21,wherein the water produced by the method has a dissolved phosphorusconcentration of about 0.0001 ppm to 0.05 ppm.

Embodiment 23 provides the method of any one of Embodiments 1-22,wherein the water produced by the method has a reactive phosphorusconcentration of about 0 ppm to about 1 ppm.

Embodiment 24 provides the method of any one of Embodiments 1-23,wherein the water produced by the method has a reactive phosphorusconcentration of about 0.0001 ppm to 0.1 ppm.

Embodiment 25 provides the method of any one of Embodiments 1-24,wherein the water produced by the method has a reactive phosphorusconcentration of about 0.0001 ppm to 0.05 ppm.

Embodiment 26 provides the method of any one of Embodiments 1-25,wherein the water produced by the method has a total nitrogenconcentration of about 0 ppm to about 2 ppm.

Embodiment 27 provides the method of any one of Embodiments 1-26,wherein the water produced by the method has a total nitrogenconcentration of about 0 ppm to about 1 ppm.

Embodiment 28 provides the method of any one of Embodiments 1-27,wherein the water produced by the method has a dissolved nitrogenconcentration of about 0 ppm to about 2 ppm.

Embodiment 29 provides the method of any one of Embodiments 1-28,wherein the water produced by the method has a dissolved nitrogenconcentration of about 0 ppm to about 1 ppm.

Embodiment 30 provides the method of any one of Embodiments 1-29,wherein raising pH of the water to precipitate the phosphorus salt fromthe water comprises raising the pH of the water to 7.5 to 12.

Embodiment 31 provides the method of any one of Embodiments 1-30,wherein raising pH of the water to precipitate the phosphorus salt fromthe water comprises raising the pH of the water to 8.5 to 9.5.

Embodiment 32 provides the method of any one of Embodiments 1-31,wherein raising pH of the water to precipitate the phosphorus salt fromthe water comprises adding one or more bases to the water.

Embodiment 33 provides the method of any one of Embodiments 1-32,wherein raising pH of the water to precipitate the phosphorus salt fromthe water comprises adding one or more flocculants to the water.

Embodiment 34 provides the method of any one of Embodiments 1-33,wherein removing the precipitated phosphorus salt from the watercomprises decantation, settling, filtration, or a combination thereof.

Embodiment 35 provides the method of any one of Embodiments 1-34,wherein the precipitated phosphorus salt comprises struvite, calciumphosphate, or a combination thereof.

Embodiment 36 provides the method of any one of Embodiments 1-35,wherein the elevated pH phosphorus removal stage removes 70-100% of thereactive phosphorus in the water.

Embodiment 37 provides the method of any one of Embodiments 1-36,wherein the elevated pH phosphorus removal stage removes 90-98% ofreactive phosphorus in the water.

Embodiment 38 provides the method of any one of Embodiments 1-37,wherein the elevated pH phosphorus removal stage removes 0-60% ofammonia in the water.

Embodiment 39 provides the method of any one of Embodiments 1-38,wherein the elevated pH phosphorus removal stage removes 20-30% ofammonia in the water.

Embodiment 40 provides the method of any one of Embodiments 1-39,wherein the elevated pH phosphorus removal stage comprises raising pH ofthe water using one or more bases to 8.5 to 9.5 and removingprecipitated phosphorus salt using decantation, settling, filtration, ora combination thereof, the precipitated phosphorus salt comprisingstruvite, calcium phosphate, or a combination thereof, wherein theelevated pH phosphorus removal stage removes 90-98% of reactivephosphorus in the water.

Embodiment 41 provides the method of any one of Embodiments 1-40,wherein the water is passed through a plurality of the electrolyticcells.

Embodiment 42 provides the method of any one of Embodiments 1-41,wherein passing the water through the electrolytic cell comprisespartially submerging the electrolytic cell in the water.

Embodiment 43 provides the method of any one of Embodiments 1-42,wherein passing the water through the electrolytic cell comprisescompletely immersing the electrolytic cell in the water.

Embodiment 44 provides the method of any one of Embodiments 1-43,further comprising applying shear to the water as it is passed throughthe electrolytic cell.

Embodiment 45 provides the method of any one of Embodiments 1-44,wherein the water is passed around and between an anode and cathode ofthe electrolytic cell.

Embodiment 46 provides the method of any one of Embodiments 1-45,wherein the water passed through the electrolytic cell has a pH of 6 to12.

Embodiment 47 provides the method of any one of Embodiments 1-46,wherein the water passed through the electrolytic cell has a pH of 6 to7.

Embodiment 48 provides the method of any one of Embodiments 1-47,further comprising adding one or more bases to the water to regulate pHof the water contacting the electrolytic cell.

Embodiment 49 provides the method of any one of Embodiments 1-48,comprising operating the electrolytic cell with DC current.

Embodiment 50 provides the method of any one of Embodiments 1-49,comprising operating the electrolytic cell with AC current.

Embodiment 51 provides the method of any one of Embodiments 1-50,comprising operating the electrolytic cell with a current density of0.001-0.1 A/cm².

Embodiment 52 provides the method of any one of Embodiments 1-51,comprising operating the electrolytic cell with a current density of0.02-0.04 A/cm².

Embodiment 53 provides the method of any one of Embodiments 1-52,wherein the electrolytic cell comprises an anode and a cathode having aspacing therebetween of 0.5-8 mm.

Embodiment 54 provides the method of any one of Embodiments 1-53,wherein the electrolytic cell comprises an anode and a cathode having aspacing therebetween of 2-4 mm.

Embodiment 55 provides the method of any one of Embodiments 1-54,wherein the electrolytic cell comprises a cathode comprising titanium,stainless steel, or a combination thereof.

Embodiment 56 provides the method of any one of Embodiments 1-55,wherein the electrolytic cell comprises a cathode comprising stainlesssteel.

Embodiment 57 provides the method of any one of Embodiments 1-56,wherein the electrolytic cell comprises an anode comprising

-   -   titanium oxide, ruthenium oxide, and iridium oxide supported on        titanium (TiO₂—RuO₂—IrO₂/Ti), or    -   titanium oxide and ruthenium oxide supported on titanium        (TiO₂—RuO₂/Ti), or    -   titanium and platinum (Ti—Pt), or    -   a combination thereof.

Embodiment 58 provides the method of any one of Embodiments 1-57,wherein the removing of nitrogen as nitrogen gas comprises convertingammonia in the water to nitrogen gas using the electrolytic cell.

Embodiment 59 provides the method of any one of Embodiments 1-58,wherein passing the water through the electrolytic nitrogen removalstage produces hypochlorite which reacts with ammonia in the water toform the nitrogen gas.

Embodiment 60 provides the method of any one of Embodiments 1-59,further comprising releasing the nitrogen gas to the atmosphere.

Embodiment 61 provides the method of any one of Embodiments 1-60,wherein passing the water through the electrolytic nitrogen removalstage removes 80-100% of ammonia from the water.

Embodiment 62 provides the method of any one of Embodiments 1-61,wherein passing the water through the electrolytic nitrogen removalstage removes 99-100% of ammonia from the water.

Embodiment 63 provides the method of any one of Embodiments 1-62,wherein passing the water through the electrolytic nitrogen removalstage removes 0.1 to 90% of reactive phosphorus from the water.

Embodiment 64 provides the method of any one of Embodiments 1-63,wherein passing the water through the electrolytic nitrogen removalstage removes 1-30% of reactive phosphorus from the water.

Embodiment 65 provides the method of any one of Embodiments 1-64,wherein the electrolytic cell produces 100-20,000 ppm of hypochloritefrom chloride in the water.

Embodiment 66 provides the method of any one of Embodiments 1-65,wherein the electrolytic cell produces 2000-2500 ppm hypochlorite fromchloride in the water.

Embodiment 67 provides the method of any one of Embodiments 1-66,wherein:

-   -   wherein passing the water through the electrolytic nitrogen        removal stage produces hypochlorite which reacts with ammonia in        the water to form the nitrogen gas;    -   the cathode comprising stainless steel;    -   the anode comprises titanium oxide, ruthenium oxide, and iridium        oxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti); and    -   passing the water through the electrolytic nitrogen removal        stage removes 80-100% of ammonia from the water.

Embodiment 68 provides the method of any one of Embodiments 1-67,wherein the anode and the cathode of the galvanic cell directly contactone another.

Embodiment 69 provides the method of any one of Embodiments 1-68,wherein the galvanic cell further comprises a conductive connector thatelectrically connects the anode and the cathode, the conductiveconnector comprising Cu, Zn, Fe, Cd, Ni, Sn, Pb, or a combinationthereof.

Embodiment 70 provides the method of Embodiment 69, wherein theconductive connector comprises brass.

Embodiment 71 provides the method of any one of Embodiments 1-70,wherein the galvanic phosphorus removal stage:

-   -   reduces total phosphorus concentration of the water by about 80%        to about 100%, or    -   reduces dissolved phosphorus concentration of the water by about        80% to about 100%, or    -   reduces reactive phosphorus concentration of the water by about        80% to about 100%, or    -   reduces total nitrogen concentration of the water by about 70%        to about 100%, or    -   reduces a dissolved nitrogen concentration of the water by about        70% to about 100%, or    -   a combination thereof.

Embodiment 72 provides the method of any one of Embodiments 1-71,wherein the salt comprising the phosphorus comprises a material from theanode of the galvanic cell.

Embodiment 73 provides the method of any one of Embodiments 1-72,further comprising applying mechanical force to the galvanic cell duringthe immersing of the galvanic cell in the water, or applying shear tothe water during the immersing of the galvanic cell in the water, or acombination thereof, wherein the mechanical force and/or shear issufficient to

-   -   dislodge at least some bubbles comprising H2 from the surface of        the anode, cathode, or a combination thereof, or    -   at least partially prevent oxide formation at the surface of the        anode, or    -   at least partially prevent agglomeration of the salt comprising        the phosphorus on the surface of the anode, or    -   a combination thereof.

Embodiment 74 provides the method of any one of Embodiments 1-73,further comprising forming a salt comprising nitrogen from the waterduring the immersing of the galvanic cell in the water, wherein theseparating of the salt comprising the phosphorus from the treated waterfurther comprises separating the salt comprising the nitrogen from thetreated water.

Embodiment 75 provides the method of any one of Embodiments 1-74,wherein the cathode comprises Cu and the anode comprises Mg.

Embodiment 76 provides the method of any one of Embodiments 1-75,wherein the cathode comprises Cu and the anode comprises Al.

Embodiment 77 provides the method of any one of Embodiments 1-76,wherein the cathode comprises a planar frame of the galvanic cell and acathode material comprised within a perimeter of the frame, wherein thecathode material is electrically connected to the frame, wherein thecathode material comprised within the perimeter of the planar framecomprises a porous cathode material.

Embodiment 78 provides the method of any one of Embodiments 1-77,comprising

-   -   immersing one or more of the galvanic cells in an enclosure        comprising the water;    -   filtering the salt comprising the phosphorus from the treated        water via one of more filters that are at least partially        submerged in the water that immerses the galvanic cells.

Embodiment 79 provides the method of any one of Embodiments 1-78,wherein

-   -   the cathode of the galvanic cell comprises a planar frame of the        galvanic cell having a polygonal perimeter and a porous material        comprised within the perimeter of the frame that is a wire mesh        or a wire screen that is in direct contact with the frame; and    -   the planar frame comprises a plurality of the anodes fastened to        the frame, and a plurality of conductive connectors that        electrically connect the anode and the cathode, the conductive        connector comprising Cu, Zn, Fe, Cd, Ni, Sn, Pb, or a        combination thereof;    -   wherein each anode is a strip fastened to the planar frame at        two opposite edges of the planar frame on a face of the frame,        wherein each of the anodes is fastened to the planar frame with        at least one of the conductive connectors at each of the two        edges of the planar frame, such that each of the anodes on the        face are approximately parallel to one another on the face and        span across the porous material comprised within the perimeter        of the planar frame forming a gap between the porous material        comprised within the perimeter of the planar frame and the anode        strip, wherein each anode directly contacts the planar frame at        each of the edges of the planar frame where the anode is        fastened to the planar frame via the at least one conductive        connector, wherein the plurality of the anodes are spaced-apart        across the face of the such that they do not physically contact        one another, and wherein the gap is about 1 mm to about 110 mm.

Embodiment 80 provides the method of any one of Embodiments 1-79,wherein:

-   -   the water immersing the galvanic cell has a pH of about 5 to        about 7;    -   the salt comprising the phosphorus formed in the galvanic        phosphorus removal stage comprises        -   AlPO₄ or a hydrate thereof, the AlPO₄ comprising the            phosphorus and Al from the anode,        -   aluminum hydroxide or a hydrate thereof, the aluminum            hydroxide comprising Al from the anode, or        -   a combination thereof;    -   the anode of the galvanic cell comprises Al, wherein the anode        is about 90 wt % to about 100 wt % Al;    -   the cathode of the galvanic cell comprises Cu, wherein the        cathode is about 90 wt % to about 100 wt % Cu; and    -   the galvanic cell comprises a conductive connector that        electrically connects the anode and the cathode, the conductive        connector comprising an alloy comprising Cu and Zn.

Embodiment 81 provides the method of any one of Embodiments 1-79,wherein:

-   -   the water immersing the galvanic cell has a pH of about 10 to        about 11;    -   the salt comprising the phosphorus formed in the galvanic        phosphorus removal stage comprises        -   magnesium phosphate, magnesium potassium phosphate, a            hydrate thereof, or a combination thereof,        -   NH₄MgPO₄ or a hydrate thereof, the NH₄MgPO₄ comprising the            phosphorus and Mg from the anode,        -   Mg(OH)₂ comprising Mg from the anode, or        -   a combination thereof;    -   the anode of the galvanic cell comprises Mg, wherein the anode        is about 90 wt % to about 100 wt % Mg;    -   the cathode of the galvanic cell comprises Cu, wherein the        cathode is about 90 wt % to about 100 wt % Cu; and    -   the galvanic cell comprises a conductive connector that        electrically connects the anode and the cathode, the conductive        connector comprising an alloy comprising Cu and Zn.

Embodiment 82 provides the method of any one of Embodiments 1-81,further comprising further removing nitrogen from water produced by thegalvanic phosphorus removal stage.

Embodiment 83 provides the method of Embodiment 82, wherein the furtherremoving nitrogen comprises exposing the water to denitrifying bacteriato convert water-soluble nitrogen therein to nitrogen gas that isremoved.

Embodiment 84 provides the method of any one of Embodiments 82-83,comprising deoxygenating the water prior to the further removing ofnitrogen therefrom.

Embodiment 85 provides the method of any one of Embodiments 82-84,comprising oxidizing or hydrolyzing at least some nitrogen in the waterto form nitrate prior to the further removing of nitrogen therefrom.

Embodiment 86 provides the method of any one of Embodiments 82-85,comprising reoxygenating the water after the further removing ofnitrogen therefrom

Embodiment 87 provides the method of any one of Embodiments 1-86,further comprising removing nitrogen from water produced by the galvanicphosphorus removal stage, the further removing nitrogen comprising:

-   -   optionally oxidizing or hydrolyzing at least some nitrogen in        the water to form nitrate;    -   optionally deoxygenating the water to an oxygen concentration of        about 0 ppm to about 0.3 ppm;    -   exposing the water to denitrifying bacteria immobilized on a        porous substrate, to convert nitrate in the water to nitrogen        gas that is removed and to form a denitrified water; and    -   optionally reoxygenating the denitrified water to an oxygen        concentration of about 1 ppm to about 20 ppm;    -   wherein the denitrified water has a total nitrogen concentration        that is about 0.0 ppm to about 2 ppm total nitrogen.

Embodiment 88 provides a method of removing phosphorus and nitrogen fromwater, the method comprising:

-   -   passing starting material water comprising nitrogen and        phosphorus through an elevated pH phosphorus removal stage,        comprising        -   raising pH of the water using one or more bases to 8.5 to            9.5 to precipitate a phosphorus salt from the water            comprising struvite, calcium phosphate, or a combination            thereof; and        -   removing the precipitated phosphorus salt from the water,            wherein the elevated pH phosphorus removal stage removes            90-98% of reactive phosphorus in the water;    -   passing the water through an electrolytic nitrogen removal stage        comprising        -   passing the water through an electrolytic cell to remove            nitrogen from the water as nitrogen gas, the electrolytic            cell comprising a cathode comprising stainless steel and an            anode that comprises titanium oxide, ruthenium oxide, and            iridium oxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti),            wherein passing the water through the electrolytic nitrogen            removal stage removes 80-100% of ammonia from the water; and    -   passing the water through a galvanic phosphorus removal stage        comprising        -   immersing a galvanic cell in the water to form treated water            comprising a salt that comprises phosphorus from the water,            the salt comprising            -   AlPO₄ or a hydrate thereof, the AlPO₄ comprising the                phosphorus and Al from the anode,            -   aluminum hydroxide or a hydrate thereof, the aluminum                hydroxide comprising Al from the anode, or            -   a combination thereof;        -   the galvanic cell comprising            -   an anode comprising Al, wherein the anode is about 90 wt                % to about 100 wt % Al,            -   a cathode comprising Cu, wherein the cathode is about 90                wt % to about 100 wt % Cu,            -   a conductive connector that electrically connects the                anode and the cathode, the conductive connector                comprising an alloy comprising Cu and Zn        -   separating the salt comprising the phosphorus from the            treated water;    -   wherein the water produced by the method has a lower phosphorus        concentration and a lower nitrogen concentration than the        starting material water, wherein the water produced by the        method has        -   a total phosphorus concentration of about 0.0001 ppm to 0.05            ppm, and        -   a total nitrogen concentration of about 0 ppm to about 1            ppm.

Embodiment 89 provides a method of removing nitrogen from water, themethod comprising:

-   -   passing the water through an electrolytic cell to remove        nitrogen from the water as nitrogen gas.

Embodiment 90 provides the method of Embodiment 89, wherein prior topassing through the electrolytic cell the water has a chlorideconcentration of 50 ppm to 40,000 ppm.

Embodiment 91 provides the method of any one of Embodiments 89-90,wherein prior to passing through the electrolytic cell the water has achloride concentration of 200 ppm to 10,000 ppm.

Embodiment 92 provides the method of any one of Embodiments 89-91,wherein the water is passed through a plurality of the electrolyticcells.

Embodiment 93 provides the method of any one of Embodiments 89-92,wherein passing the water through the electrolytic cell comprisespartially submerging the electrolytic cell in the water.

Embodiment 94 provides the method of any one of Embodiments 89-93,wherein passing the water through the electrolytic cell comprisescompletely immersing the electrolytic cell in the water.

Embodiment 95 provides the method of any one of Embodiments 89-94,further comprising applying shear to the water as it is passed throughthe electrolytic cell.

Embodiment 96 provides the method of any one of Embodiments 89-95,wherein the water is passed around and between an anode and cathode ofthe electrolytic cell.

Embodiment 97 provides the method of any one of Embodiments 89-96,wherein the water passed through the electrolytic cell has a pH of 6 to12.

Embodiment 98 provides the method of any one of Embodiments 89-97,wherein the water passed through the electrolytic cell has a pH of 6 to7.

Embodiment 99 provides the method of any one of Embodiments 89-98,further comprising adding one or more bases to the water to regulate pHof the water contacting the electrolytic cell.

Embodiment 100 provides the method of any one of Embodiments 89-99,comprising operating the electrolytic cell with DC current.

Embodiment 101 provides the method of any one of Embodiments 89-100,comprising operating the electrolytic cell with AC current.

Embodiment 102 provides the method of any one of Embodiments 89-101,comprising operating the electrolytic cell with a current density of0.001-0.1 A/cm².

Embodiment 103 provides the method of any one of Embodiments 89-102,comprising operating the electrolytic cell with a current density of0.02-0.04 A/cm².

Embodiment 104 provides the method of any one of Embodiments 89-103,wherein the electrolytic cell comprises an anode and a cathode having aspacing therebetween of 0.5-8 mm.

Embodiment 105 provides the method of any one of Embodiments 89-104,wherein the electrolytic cell comprises an anode and a cathode having aspacing therebetween of 2-4 mm.

Embodiment 106 provides the method of any one of Embodiments 89-105,wherein the electrolytic cell comprises a cathode comprising titanium,stainless steel, or a combination thereof.

Embodiment 107 provides the method of any one of Embodiments 89-106,wherein the electrolytic cell comprises a cathode comprising stainlesssteel.

Embodiment 108 provides the method of any one of Embodiments 89-107,wherein the electrolytic cell comprises an anode comprising

-   -   titanium oxide, ruthenium oxide, and iridium oxide supported on        titanium (TiO₂—RuO₂—IrO₂/Ti), or    -   titanium oxide and ruthenium oxide supported on titanium        (TiO₂—RuO₂/Ti), or    -   titanium and platinum (Ti—Pt), or    -   a combination thereof.

Embodiment 109 provides the method of any one of Embodiments 89-108,wherein the removing of nitrogen as nitrogen gas comprises convertingammonia in the water to nitrogen gas using the electrolytic cell.

Embodiment 110 provides the method of any one of Embodiments 89-109,wherein passing the water through the electrolytic nitrogen removalstage produces hypochlorite which reacts with ammonia in the water toform the nitrogen gas.

Embodiment 111 provides the method of any one of Embodiments 89-110,further comprising releasing the nitrogen gas to the atmosphere.

Embodiment 112 provides the method of any one of Embodiments 89-111,wherein passing the water through the electrolytic nitrogen removalstage removes 80-100% of ammonia from the water.

Embodiment 113 provides the method of any one of Embodiments 89-112,wherein passing the water through the electrolytic nitrogen removalstage removes 99-100% of ammonia from the water.

Embodiment 114 provides the method of any one of Embodiments 89-113,wherein passing the water through the electrolytic nitrogen removalstage removes 0.1 to 90% of reactive phosphorus from the water.

Embodiment 115 provides the method of any one of Embodiments 89-114,wherein passing the water through the electrolytic nitrogen removalstage removes 1-30% of reactive phosphorus from the water.

Embodiment 116 provides the method of any one of Embodiments 89-115,wherein the electrolytic cell produces 100-20,000 ppm of hypochloritefrom chloride in the water.

Embodiment 117 provides the method of any one of Embodiments 89-116,wherein the electrolytic cell produces 2000-2500 ppm hypochlorite fromchloride in the water.

Embodiment 118 provides the method of any one of Embodiments 89-117,wherein:

-   -   wherein passing the water through the electrolytic nitrogen        removal stage produces hypochlorite which reacts with ammonia in        the water to form the nitrogen gas;    -   the cathode comprising stainless steel;    -   the anode comprises titanium oxide, ruthenium oxide, and iridium        oxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti); and    -   passing the water through the electrolytic nitrogen removal        stage removes 80-100% of ammonia from the water.

Embodiment 119 provides a method of removing nitrogen from water, themethod comprising:

-   -   passing the water through an electrolytic cell to remove        nitrogen from the water as nitrogen gas, the electrolytic cell        comprising a cathode comprising stainless steel and/or titanium        and an anode comprising        -   titanium oxide, ruthenium oxide, and iridium oxide supported            on titanium (TiO₂—RuO₂—IrO₂/Ti), or        -   titanium oxide and ruthenium oxide supported on titanium            (TiO₂—RuO₂/Ti), or        -   titanium and platinum (Ti—Pt), or        -   a combination thereof;    -   wherein the removal of nitrogen as nitrogen gas removes 80-100%        of ammonia from the water.

Embodiment 120 provides a system for removal of nitrogen and phosphorusfrom water, the system comprising:

-   -   an elevated pH phosphorus removal stage configured to raise pH        of starting material water to greater than or equal to 7.5 to        precipitate a phosphorus salt from the water and configured to        remove the precipitated phosphorus salt from the water;    -   an electrolytic nitrogen removal stage comprising an        electrolytic cell configured to remove nitrogen from the water        as nitrogen gas; and    -   a galvanic phosphorus removal stage comprising a galvanic cell        comprising an anode comprising Mg, Al, Fe, Zn, or a combination        thereof, and a cathode having a different composition than the        anode, the cathode comprising Cu, Ni, Fe, or a combination        thereof, the galvanic cell configured to form a treated water        comprising a salt that comprises phosphorus from the water,        wherein the galvanic phosphorus removal stage is configured to        separate the salt comprising the phosphorus from the treated        water;    -   wherein the water produced by the system has a lower phosphorus        concentration and a lower nitrogen concentration than the        starting material water.

Embodiment 121 provides an apparatus for removal of nitrogen from water,the apparatus comprising:

-   -   an electrolytic cell through which water is configured to be        flowed to remove nitrogen from the water as nitrogen gas, the        electrolytic cell comprising a cathode comprising stainless        steel and an anode comprising        -   titanium oxide, ruthenium oxide, and iridium oxide supported            on titanium (TiO₂—RuO₂—IrO₂/Ti), or        -   titanium oxide and ruthenium oxide supported on titanium            (TiO₂—RuO₂/Ti), or        -   titanium and platinum (Ti—Pt), or        -   a combination thereof;    -   wherein the removal of nitrogen as nitrogen gas removes 80-100%        of ammonia from the water.

Embodiment 122 provides the method, system, or apparatus of any one orany combination of Embodiments 1-121 optionally configured such that allelements or options recited are available to use or select from.

What is claimed is:
 1. A method of removing phosphorus and nitrogen fromwater, the method comprising: passing starting material water comprisingnitrogen and phosphorus through an elevated pH phosphorus removal stagecomprising raising pH of the water to greater than or equal to 7.5 toprecipitate a phosphorus salt from the water; and removing theprecipitated phosphorus salt from the water; passing the water throughan electrolytic nitrogen removal stage comprising passing the waterthrough an electrolytic cell to remove nitrogen from the water asnitrogen gas; and passing the water through a galvanic phosphorusremoval stage comprising immersing a galvanic cell in the water to formtreated water comprising a salt that comprises phosphorus from thewater, the galvanic cell comprising an anode comprising Mg, Al, Fe, Zn,or a combination thereof, a cathode having a different composition thanthe anode, the cathode comprising Cu, Ni, Fe, or a combination thereof;and separating the salt comprising the phosphorus from the treatedwater; wherein the water produced by the method has a lower phosphorusconcentration and a lower nitrogen concentration than the startingmaterial water.
 2. The method of claim 1, wherein the starting materialwater is water originated from a process of dissolvingphosphate-containing rock to produce phosphoric acid.
 3. The method ofclaim 1, wherein the starting material water has a chlorideconcentration of 200 ppm to 10,000 ppm.
 4. The method of claim 1,wherein the water produced by the method has a total phosphorusconcentration, a dissolved phosphorus concentration, a reactivephosphorus concentration, or a combination thereof, of 0.0001 ppm to 0.1ppm, and a total nitrogen concentration, a dissolved nitrogenconcentration, or a combination thereof, of about 0 ppm to about 1 ppm.5. The method of claim 1, wherein raising pH of the water to precipitatethe phosphorus salt from the water comprises raising the pH of the waterto 8.5 to 9.5.
 6. The method of claim 1, wherein the precipitatedphosphorus salt comprises struvite, calcium phosphate, or a combinationthereof.
 7. The method of claim 1, wherein the electrolytic cellcomprises a cathode comprising titanium, stainless steel, or acombination thereof.
 8. The method of claim 1, wherein the electrolyticcell comprises an anode comprising titanium oxide, ruthenium oxide, andiridium oxide supported on titanium (TiO₂—RuO₂—IrO₂/Ti), or titaniumoxide and ruthenium oxide supported on titanium (TiO₂—RuO₂/Ti), ortitanium and platinum (Ti—Pt), or a combination thereof.
 9. The methodof claim 1, wherein the removing of nitrogen as nitrogen gas comprisesconverting ammonia in the water to nitrogen gas using the electrolyticcell, wherein passing the water through the electrolytic nitrogenremoval stage produces hypochlorite which reacts with ammonia in thewater to form the nitrogen gas.
 10. The method of claim 1, wherein thesalt comprising the phosphorus comprises a material from the anode ofthe galvanic cell.
 11. The method of claim 1, wherein the cathodecomprises Cu and the anode comprises Mg.
 12. The method of claim 1,wherein the cathode comprises Cu and the anode comprises Al.
 13. Themethod of claim 1, wherein: the water immersing the galvanic cell has apH of about 5 to about 7; the salt comprising the phosphorus formed inthe galvanic phosphorus removal stage comprises AlPO₄ or a hydratethereof, the AlPO₄ comprising the phosphorus and Al from the anode,aluminum hydroxide or a hydrate thereof, the aluminum hydroxidecomprising Al from the anode, or a combination thereof; the anode of thegalvanic cell comprises Al, wherein the anode is about 90 wt % to about100 wt % Al; the cathode of the galvanic cell comprises Cu, wherein thecathode is about 90 wt % to about 100 wt % Cu; and the galvanic cellcomprises a conductive connector that electrically connects the anodeand the cathode, the conductive connector comprising an alloy comprisingCu and Zn.
 14. The method of claim 1, wherein: the water immersing thegalvanic cell has a pH of about 10 to about 11; the salt comprising thephosphorus formed in the galvanic phosphorus removal stage comprisesmagnesium phosphate, magnesium potassium phosphate, a hydrate thereof,or a combination thereof, NH₄MgPO₄ or a hydrate thereof, the NH₄MgPO₄comprising the phosphorus and Mg from the anode, Mg(OH)₂ comprising Mgfrom the anode, or a combination thereof; the anode of the galvanic cellcomprises Mg, wherein the anode is about 90 wt % to about 100 wt % Mg;the cathode of the galvanic cell comprises Cu, wherein the cathode isabout 90 wt % to about 100 wt % Cu; and the galvanic cell comprises aconductive connector that electrically connects the anode and thecathode, the conductive connector comprising an alloy comprising Cu andZn.
 15. The method of claim 1, further comprising further removingnitrogen from water produced by the galvanic phosphorus removal stage.16. A method of removing phosphorus and nitrogen from water, the methodcomprising: passing starting material water comprising nitrogen andphosphorus through an elevated pH phosphorus removal stage, comprisingraising pH of the water using one or more bases to 8.5 to 9.5 toprecipitate a phosphorus salt from the water comprising struvite,calcium phosphate, or a combination thereof; and removing theprecipitated phosphorus salt from the water, wherein the elevated pHphosphorus removal stage removes 90-98% of reactive phosphorus in thewater; passing the water through an electrolytic nitrogen removal stagecomprising passing the water through an electrolytic cell to removenitrogen from the water as nitrogen gas, the electrolytic cellcomprising a cathode comprising stainless steel and an anode thatcomprises titanium oxide, ruthenium oxide, and iridium oxide supportedon titanium (TiO₂—RuO₂—IrO₂/Ti), wherein passing the water through theelectrolytic nitrogen removal stage removes 80-100% of ammonia from thewater; and passing the water through a galvanic phosphorus removal stagecomprising immersing a galvanic cell in the water to form treated watercomprising a salt that comprises phosphorus from the water, the saltcomprising AlPO₄ or a hydrate thereof, the AlPO₄ comprising thephosphorus and Al from the anode, aluminum hydroxide or a hydratethereof, the aluminum hydroxide comprising Al from the anode, or acombination thereof; the galvanic cell comprising an anode comprisingAl, wherein the anode is about 90 wt % to about 100 wt % Al, a cathodecomprising Cu, wherein the cathode is about 90 wt % to about 100 wt %Cu, a conductive connector that electrically connects the anode and thecathode, the conductive connector comprising an alloy comprising Cu andZn separating the salt comprising the phosphorus from the treated water;wherein the water produced by the method has a lower phosphorusconcentration and a lower nitrogen concentration than the startingmaterial water, wherein the water produced by the method has a totalphosphorus concentration of about 0.0001 ppm to 0.05 ppm, and a totalnitrogen concentration of about 0 ppm to about 1 ppm.
 17. A method ofremoving nitrogen from water, the method comprising: passing the waterthrough an electrolytic cell to remove nitrogen from the water asnitrogen gas.
 18. The method of claim 17, wherein: passing the waterthrough the electrolytic nitrogen removal stage produces hypochloritewhich reacts with ammonia in the water to form the nitrogen gas; thecathode comprises stainless steel; the anode comprises titanium oxide,ruthenium oxide, and iridium oxide supported on titanium(TiO₂—RuO₂—IrO₂/Ti), or titanium oxide and ruthenium oxide supported ontitanium (TiO₂—RuO₂/Ti), or titanium and platinum (Ti—Pt), or acombination thereof; and passing the water through the electrolyticnitrogen removal stage removes 80-100% of ammonia from the water.
 19. Asystem for removal of nitrogen and phosphorus from water for performingthe method of claim 1, the system comprising: an elevated pH phosphorusremoval stage configured to raise pH of starting material water togreater than or equal to 7.5 to precipitate a phosphorus salt from thewater and configured to remove the precipitated phosphorus salt from thewater; an electrolytic nitrogen removal stage comprising an electrolyticcell configured to remove nitrogen from the water as nitrogen gas; and agalvanic phosphorus removal stage comprising a galvanic cell comprisingan anode comprising Mg, Al, Fe, Zn, or a combination thereof, and acathode having a different composition than the anode, the cathodecomprising Cu, Ni, Fe, or a combination thereof, the galvanic cellconfigured to form a treated water comprising a salt that comprisesphosphorus from the water, wherein the galvanic phosphorus removal stageis configured to separate the salt comprising the phosphorus from thetreated water; wherein the water produced by the system has a lowerphosphorus concentration and a lower nitrogen concentration than thestarting material water.
 20. An apparatus for removal of nitrogen fromwater for performing the method of claim 17, the apparatus comprising:an electrolytic cell through which water is configured to be flowed toremove nitrogen from the water as nitrogen gas, the electrolytic cellcomprising a cathode comprising stainless steel and an anode comprisingtitanium oxide, ruthenium oxide, and iridium oxide supported on titanium(TiO₂—RuO₂—IrO₂/Ti), or titanium oxide and ruthenium oxide supported ontitanium (TiO₂—RuO₂/Ti), or titanium and platinum (Ti—Pt), or acombination thereof; wherein the removal of nitrogen as nitrogen gasremoves 80-100% of ammonia from the water.